EP4079743A1

EP4079743A1 - Organic electroluminescent materials and devices

Info

Publication number: EP4079743A1
Application number: EP22169225.4A
Authority: EP
Inventors: Bin Ma; Bert Alleyne; Pierre-Luc T. Boudreault
Original assignee: Universal Display Corp
Current assignee: Universal Display Corp
Priority date: 2021-04-23
Filing date: 2022-04-21
Publication date: 2022-10-26
Also published as: US20220407020A1; CN115304645A; KR20220146347A

Abstract

A heteroleptic compound having a Formula Ir(LA)m(LB)3-m, having a structure of Formula Iis disclosed. In Formula I, m is 1 or 2; moieties A, C, and D are each independently monocyclic rings or polycyclic fused ring structures; each R1, R2, RA, RB, RC, RD, and RE is independently hydrogen or a substituent; if moiety A is a monocyclic 6-membered ring, then the RA para to N of ring A is not an aryl group; at least one of R1 and R2 is selected from the group consisting of aryl, heteroaryl, cycloalkyl, heterocycloalkyl, and combinations thereof; and adjacent substituents can be joined to form a ring. OLEDs, consumer products, and formulations including the heteroleptic compound are also disclosed.

Description

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims priority under 35 U.S.C. § 119(e) to United States Provisional Applications No. 63/195,451, filed on June 1, 2021 , No. 63/214,086, filed on June 23, 2021 , No. 63/182,350, filed on April 30, 2021 , and No. 63/178,673, filed on April 23, 2021 , the entire contents of which are incorporated herein by reference

FIELD

The present disclosure generally relates to organometallic compounds and formulations and their various uses including as emitters in devices such as organic light emitting diodes and related electronic devices.

BACKGROUND

Opto-electronic devices that make use of organic materials are becoming increasingly desirable for various reasons. Many of the materials used to make such devices are relatively inexpensive, so organic opto-electronic devices have the potential for cost advantages over inorganic devices. In addition, the inherent properties of organic materials, such as their flexibility, may make them well suited for particular applications such as fabrication on a flexible substrate. Examples of organic opto-electronic devices include organic light emitting diodes/devices (OLEDs), organic phototransistors, organic photovoltaic cells, and organic photodetectors. For OLEDs, the organic materials may have performance advantages over conventional materials.
OLEDs make use of thin organic films that emit light when voltage is applied across the device. OLEDs are becoming an increasingly interesting technology for use in applications such as flat panel displays, illumination, and backlighting.
One application for phosphorescent emissive molecules is a full color display. Industry standards for such a display call for pixels adapted to emit particular colors, referred to as "saturated" colors. In particular, these standards call for saturated red, green, and blue pixels. Alternatively, the OLED can be designed to emit white light. In conventional liquid crystal displays emission from a white backlight is filtered using absorption filters to produce red, green and blue emission. The same technique can also be used with OLEDs. The white OLED can be either a single emissive layer (EML) device or a stack structure. Color may be measured using CIE coordinates, which are well known to the art.

SUMMARY

In one aspect, the present disclosure provides a heteroleptic compound having a Formula Ir(L_A)_m(L_B)_3-m, having a structure of Formula I
In Formula I:

m is 1 or 2;
moieties A, C, and D are each independently a monocyclic ring or a polycyclic fused ring structure, both comprising 5-membered and/or 6-membered aromatic rings;
each of R^A, R^B, R^C, R^D, and R^E independently represents mono to the maximum allowable substitution, or no substitution;
each R¹, R², R^A, R^B, R^C, R^D, and R^E is independently hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, boryl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof;
wherein if moiety A is a monocyclic 6-membered ring, then the R^A para to N of ring A is not an aryl group;
wherein L_A and L_B are different; and
at least one of R¹ and R² is selected from the group consisting of aryl, heteroaryl, cycloalkyl, heterocycloalkyl, and combinations thereof; and
two adjacent R^B, one R^A and one R^B, one R^E and one R^D, or two adjacent R¹, R², and R^E can be joined to form a ring.

In another aspect, the present disclosure provides a formulation of the compound of the present disclosure.
In yet another aspect, the present disclosure provides an OLED having an organic layer comprising the compound of the present disclosure.
In yet another aspect, the present disclosure provides a consumer product comprising an OLED with an organic layer comprising the compound of the present disclosure.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows an organic light emitting device.
FIG. 2 shows an inverted organic light emitting device that does not have a separate electron transport layer.

DETAILED DESCRIPTION

A. Terminology

Unless otherwise specified, the below terms used herein are defined as follows:
As used herein, the term "organic" includes polymeric materials as well as small molecule organic materials that may be used to fabricate organic opto-electronic devices. "Small molecule" refers to any organic material that is not a polymer, and "small molecules" may actually be quite large. Small molecules may include repeat units in some circumstances. For example, using a long chain alkyl group as a substituent does not remove a molecule from the "small molecule" class. Small molecules may also be incorporated into polymers, for example as a pendent group on a polymer backbone or as a part of the backbone. Small molecules may also serve as the core moiety of a dendrimer, which consists of a series of chemical shells built on the core moiety. The core moiety of a dendrimer may be a fluorescent or phosphorescent small molecule emitter. A dendrimer may be a "small molecule," and it is believed that all dendrimers currently used in the field of OLEDs are small molecules.
As used herein, "top" means furthest away from the substrate, while "bottom" means closest to the substrate. Where a first layer is described as "disposed over" a second layer, the first layer is disposed further away from substrate. There may be other layers between the first and second layer, unless it is specified that the first layer is "in contact with" the second layer. For example, a cathode may be described as "disposed over" an anode, even though there are various organic layers in between.
As used herein, "solution processable" means capable of being dissolved, dispersed, or transported in and/or deposited from a liquid medium, either in solution or suspension form.
A ligand may be referred to as "photoactive" when it is believed that the ligand directly contributes to the photoactive properties of an emissive material. A ligand may be referred to as "ancillary" when it is believed that the ligand does not contribute to the photoactive properties of an emissive material, although an ancillary ligand may alter the properties of a photoactive ligand.
As used herein, and as would be generally understood by one skilled in the art, a first "Highest Occupied Molecular Orbital" (HOMO) or "Lowest Unoccupied Molecular Orbital" (LUMO) energy level is "greater than" or "higher than" a second HOMO or LUMO energy level if the first energy level is closer to the vacuum energy level. Since ionization potentials (IP) are measured as a negative energy relative to a vacuum level, a higher HOMO energy level corresponds to an IP having a smaller absolute value (an IP that is less negative). Similarly, a higher LUMO energy level corresponds to an electron affinity (EA) having a smaller absolute value (an EA that is less negative). On a conventional energy level diagram, with the vacuum level at the top, the LUMO energy level of a material is higher than the HOMO energy level of the same material. A "higher" HOMO or LUMO energy level appears closer to the top of such a diagram than a "lower" HOMO or LUMO energy level.
As used herein, and as would be generally understood by one skilled in the art, a first work function is "greater than" or "higher than" a second work function if the first work function has a higher absolute value. Because work functions are generally measured as negative numbers relative to vacuum level, this means that a "higher" work function is more negative. On a conventional energy level diagram, with the vacuum level at the top, a "higher" work function is illustrated as further away from the vacuum level in the downward direction. Thus, the definitions of HOMO and LUMO energy levels follow a different convention than work functions.
The terms "halo," "halogen," and "halide" are used interchangeably and refer to fluorine, chlorine, bromine, and iodine.
The term "acyl" refers to a substituted carbonyl radical (C(O)-R_s).
The term "ester" refers to a substituted oxycarbonyl (-O-C(O)-R_s or -C(O)-O-R_s) radical.
The term "ether" refers to an -OR_s radical.
The terms "sulfanyl" or "thio-ether" are used interchangeably and refer to a -SR_s radical.
The term "selenyl" refers to a -SeR_s radical.
The term "sulfinyl" refers to a -S(O)-R_s radical.
The term "sulfonyl" refers to a -SO₂-R_s radical.
The term "phosphino" refers to a -P(R_s)₃ radical, wherein each R_s can be same or different.
The term "silyl" refers to a -Si(R_s)₃ radical, wherein each R_s can be same or different.
The term "germyl" refers to a -Ge(R_s)₃ radical, wherein each R_s can be same or different.
The term "boryl" refers to a -B(R_s)₂ radical or its Lewis adduct -B(R_s)₃ radical, wherein R_s can be same or different.
In each of the above, R_s can be hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, and combination thereof. Preferred R_s is selected from the group consisting of alkyl, cycloalkyl, aryl, heteroaryl, and combination thereof.
The term "alkyl" refers to and includes both straight and branched chain alkyl radicals. Preferred alkyl groups are those containing from one to fifteen carbon atoms and includes methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl, and the like. Additionally, the alkyl group may be optionally substituted.
The term "cycloalkyl" refers to and includes monocyclic, polycyclic, and spiro alkyl radicals. Preferred cycloalkyl groups are those containing 3 to 12 ring carbon atoms and includes cyclopropyl, cyclopentyl, cyclohexyl, bicyclo[3.1.1]heptyl, spiro[4.5]decyl, spiro[5.5]undecyl, adamantyl, and the like. Additionally, the cycloalkyl group may be optionally substituted.
The terms "heteroalkyl" or "heterocycloalkyl" refer to an alkyl or a cycloalkyl radical, respectively, having at least one carbon atom replaced by a heteroatom. Optionally the at least one heteroatom is selected from O, S, N, P, B, Si and Se, preferably, O, S or N. Additionally, the heteroalkyl or heterocycloalkyl group may be optionally substituted.
The term "alkenyl" refers to and includes both straight and branched chain alkene radicals. Alkenyl groups are essentially alkyl groups that include at least one carbon-carbon double bond in the alkyl chain. Cycloalkenyl groups are essentially cycloalkyl groups that include at least one carbon-carbon double bond in the cycloalkyl ring. The term "heteroalkenyl" as used herein refers to an alkenyl radical having at least one carbon atom replaced by a heteroatom. Optionally the at least one heteroatom is selected from O, S, N, P, B, Si, and Se, preferably, O, S, or N. Preferred alkenyl, cycloalkenyl, or heteroalkenyl groups are those containing two to fifteen carbon atoms. Additionally, the alkenyl, cycloalkenyl, or heteroalkenyl group may be optionally substituted.
The term "alkynyl" refers to and includes both straight and branched chain alkyne radicals. Alkynyl groups are essentially alkyl groups that include at least one carbon-carbon triple bond in the alkyl chain. Preferred alkynyl groups are those containing two to fifteen carbon atoms. Additionally, the alkynyl group may be optionally substituted.
The terms "aralkyl" or "arylalkyl" are used interchangeably and refer to an alkyl group that is substituted with an aryl group. Additionally, the aralkyl group may be optionally substituted.
The term "heterocyclic group" refers to and includes aromatic and non-aromatic cyclic radicals containing at least one heteroatom. Optionally the at least one heteroatom is selected from O, S, N, P, B, Si, and Se, preferably, O, S, or N. Hetero-aromatic cyclic radicals may be used interchangeably with heteroaryl. Preferred hetero-non-aromatic cyclic groups are those containing 3 to 7 ring atoms which includes at least one hetero atom, and includes cyclic amines such as morpholino, piperidino, pyrrolidino, and the like, and cyclic ethers/thio-ethers, such as tetrahydrofuran, tetrahydropyran, tetrahydrothiophene, and the like. Additionally, the heterocyclic group may be optionally substituted.
The term "aryl" refers to and includes both single-ring aromatic hydrocarbyl groups and polycyclic aromatic ring systems. The polycyclic rings may have two or more rings in which two carbons are common to two adjoining rings (the rings are "fused") wherein at least one of the rings is an aromatic hydrocarbyl group, e.g., the other rings can be cycloalkyls, cycloalkenyls, aryl, heterocycles, and/or heteroaryls. Preferred aryl groups are those containing six to thirty carbon atoms, preferably six to twenty carbon atoms, more preferably six to twelve carbon atoms. Especially preferred is an aryl group having six carbons, ten carbons or twelve carbons. Suitable aryl groups include phenyl, biphenyl, triphenyl, triphenylene, tetraphenylene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene, chrysene, perylene, and azulene, preferably phenyl, biphenyl, triphenyl, triphenylene, fluorene, and naphthalene. Additionally, the aryl group may be optionally substituted.
The term "heteroaryl" refers to and includes both single-ring aromatic groups and polycyclic aromatic ring systems that include at least one heteroatom. The heteroatoms include, but are not limited to O, S, N, P, B, Si, and Se. In many instances, O, S, or N are the preferred heteroatoms. Hetero-single ring aromatic systems are preferably single rings with 5 or 6 ring atoms, and the ring can have from one to six heteroatoms. The hetero-polycyclic ring systems can have two or more rings in which two atoms are common to two adjoining rings (the rings are "fused") wherein at least one of the rings is a heteroaryl, e.g., the other rings can be cycloalkyls, cycloalkenyls, aryl, heterocycles, and/or heteroaryls. The hetero-polycyclic aromatic ring systems can have from one to six heteroatoms per ring of the polycyclic aromatic ring system. Preferred heteroaryl groups are those containing three to thirty carbon atoms, preferably three to twenty carbon atoms, more preferably three to twelve carbon atoms. Suitable heteroaryl groups include dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridylindole, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, indoxazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuropyridine, furodipyridine, benzothienopyridine, thienodipyridine, benzoselenophenopyridine, and selenophenodipyridine, preferably dibenzothiophene, dibenzofuran, dibenzoselenophene, carbazole, indolocarbazole, imidazole, pyridine, triazine, benzimidazole, 1,2-azaborine, 1,3-azaborine, 1,4-azaborine, borazine, and aza-analogs thereof. Additionally, the heteroaryl group may be optionally substituted.
Of the aryl and heteroaryl groups listed above, the groups of triphenylene, naphthalene, anthracene, dibenzothiophene, dibenzofuran, dibenzoselenophene, carbazole, indolocarbazole, imidazole, pyridine, pyrazine, pyrimidine, triazine, and benzimidazole, and the respective aza-analogs of each thereof are of particular interest.
The terms alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aralkyl, heterocyclic group, aryl, and heteroaryl, as used herein, are independently unsubstituted, or independently substituted, with one or more general substituents.
In many instances, the general substituents are selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, germyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, selenyl, sulfinyl, sulfonyl, phosphino, boryl, and combinations thereof.
In some instances, the preferred general substituents are selected from the group consisting of deuterium, fluorine, alkyl, cycloalkyl, heteroalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, aryl, heteroaryl, nitrile, isonitrile, sulfanyl, boryl, and combinations thereof.
In some instances, the more preferred general substituents are selected from the group consisting of deuterium, fluorine, alkyl, cycloalkyl, alkoxy, aryloxy, amino, silyl, boryl, aryl, heteroaryl, sulfanyl, and combinations thereof.
In yet other instances, the most preferred general substituents are selected from the group consisting of deuterium, fluorine, alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof.
The terms "substituted" and "substitution" refer to a substituent other than H that is bonded to the relevant position, e.g., a carbon or nitrogen. For example, when R¹ represents mono-substitution, then one R¹ must be other than H (i.e., a substitution). Similarly, when R¹ represents di-substitution, then two of R¹ must be other than H. Similarly, when R¹ represents zero or no substitution, R¹, for example, can be a hydrogen for available valencies of ring atoms, as in carbon atoms for benzene and the nitrogen atom in pyrrole, or simply represents nothing for ring atoms with fully filled valencies, e.g., the nitrogen atom in pyridine. The maximum number of substitutions possible in a ring structure will depend on the total number of available valencies in the ring atoms.
As used herein, "combinations thereof' indicates that one or more members of the applicable list are combined to form a known or chemically stable arrangement that one of ordinary skill in the art can envision from the applicable list. For example, an alkyl and deuterium can be combined to form a partial or fully deuterated alkyl group; a halogen and alkyl can be combined to form a halogenated alkyl substituent; and a halogen, alkyl, and aryl can be combined to form a halogenated arylalkyl. In one instance, the term substitution includes a combination of two to four of the listed groups. In another instance, the term substitution includes a combination of two to three groups. In yet another instance, the term substitution includes a combination of two groups. Preferred combinations of substituent groups are those that contain up to fifty atoms that are not hydrogen or deuterium, or those which include up to forty atoms that are not hydrogen or deuterium, or those that include up to thirty atoms that are not hydrogen or deuterium. In many instances, a preferred combination of substituent groups will include up to twenty atoms that are not hydrogen or deuterium.
The "aza" designation in the fragments described herein, i.e. aza-dibenzofuran, aza-dibenzothiophene, etc. means that one or more of the C-H groups in the respective aromatic ring can be replaced by a nitrogen atom, for example, and without any limitation, azatriphenylene encompasses both dibenzo[f,h]quinoxaline and dibenzo[f,h]quinoline. One of ordinary skill in the art can readily envision other nitrogen analogs of the azaderivatives described above, and all such analogs are intended to be encompassed by the terms as set forth herein.
As used herein, "deuterium" refers to an isotope of hydrogen. Deuterated compounds can be readily prepared using methods known in the art. For example, U.S. Pat. No. 8,557,400 , Patent Pub. No. WO 2006/095951 , and U.S. Pat. Application Pub. No. US 2011/0037057 , which are hereby incorporated by reference in their entireties, describe the making of deuterium-substituted organometallic complexes. Further reference is made to Ming Yan, et al., Tetrahedron 2015, 71, 1425-30 and Atzrodt et al., Angew. Chem. Int. Ed. (Reviews) 2007, 46, 7744-65, which are incorporated by reference in their entireties, describe the deuteration of the methylene hydrogens in benzyl amines and efficient pathways to replace aromatic ring hydrogens with deuterium, respectively.
It is to be understood that when a molecular fragment is described as being a substituent or otherwise attached to another moiety, its name may be written as if it were a fragment (e.g. phenyl, phenylene, naphthyl, dibenzofuryl) or as if it were the whole molecule (e.g. benzene, naphthalene, dibenzofuran). As used herein, these different ways of designating a substituent or attached fragment are considered to be equivalent.
In some instance, a pair of adjacent substituents can be optionally joined or fused into a ring. The preferred ring is a five, six, or seven-membered carbocyclic or heterocyclic ring, includes both instances where the portion of the ring formed by the pair of substituents is saturated and where the portion of the ring formed by the pair of substituents is unsaturated. As used herein, "adjacent" means that the two substituents involved can be on the same ring next to each other, or on two neighboring rings having the two closest available substitutable positions, such as 2, 2' positions in a biphenyl, or 1, 8 position in a naphthalene, as long as they can form a stable fused ring system.

B. The Compounds of the Present Disclosure

m is 1 or 2;
moieties A, C, and D are each independently a monocyclic ring or a polycyclic fused ring structure, both comprising 5-membered and/or 6-membered aromatic rings;
each of R^A, R^B, R^C, R^D, and R^E independently represents mono to the maximum allowable substitution, or no substitution;
each R¹, R², R^A, R^B, R^C, R^D, and R^E is independently hydrogen or a substituent selected from the group consisting of the general substituents defined herein;
wherein if moiety A is a monocyclic 6-membered ring, then the R^A para to N of ring A is not an aryl group;
wherein L_A and L_B are different; each two L_A when m is 2 or two L_B when m is 1 can be same or different; and
at least one of R¹ and R² is selected from the group consisting of aryl, heteroaryl, cycloalkyl, heterocycloalkyl, and combinations thereof; and
two adjacent R^B, one R^A and one R^B, one R^E and one R^D, or two adjacent R¹, R², and R^E can be joined to form a ring.

In some embodiments, m in Formula I is 1, and the compound can have a structure of
In some embodiments, m in Formula I is 2, and the compound can have a structure of
In some embodiments of Formula I, one or both of R¹ and R² can be further substituted by deuterium, alkyl, and partially or fully deuterated alkyl.
In some embodiments, two adjacent R^Bs can be joined to form a ring. In some embodiments, one R^A and one R^B can be joined to form a ring. In some embodiments, one R^E and one R^D can be joined to form a ring. In some embodiments, two adjacent R¹, R², and R^E can be joined to form a ring.
In some embodiments, each R¹, R², R^A, R^B, R^C, R^D, and R^E is independently hydrogen or a substituent selected from the group consisting of the preferred general substituents defined herein. In some embodiments, each R¹, R², R^A, R^B, R^C, R^D, and R^E is independently hydrogen or a substituent selected from the group consisting of the more preferred general substituents defined herein. In some embodiments, each R¹, R², R^A, R^B, R^C, R^D, and R^E is independently hydrogen or a substituent selected from the group consisting of the Most Preferred General Substituents defined herein.
In some embodiments, moiety D is monocyclic.
In some embodiments, R¹ is selected from the group consisting of aryl, heteroaryl, cycloalkyl, heterocycloalkyl, and combinations thereof. In some embodiments, R¹ is selected from the group consisting of aryl, heteroaryl, cycloalkyl, heterocycloalkyl, and combinations thereof, and R² is hydrogen or deuterium. In some embodiments, R¹ is selected from the group consisting of aryl, heteroaryl, cycloalkyl, heterocycloalkyl, and combinations thereof, while R² is hydrogen or deuterium, and R^E is H or D. In any of these embodiments, R¹ can be further substituted by deuterium, alkyl, and partially or fully deuterated alkyl.
In some embodiments, R² is selected from the group consisting of aryl, heteroaryl, cycloalkyl, heterocycloalkyl, and combinations thereof. In some embodiments, R² is selected from the group consisting of aryl, heteroaryl, cycloalkyl, heterocycloalkyl, and combinations thereof, and R¹ is hydrogen or deuterium. In some embodiments, R² is selected from the group consisting of aryl, heteroaryl, cycloalkyl, heterocycloalkyl, and combinations thereof, while R¹ is hydrogen or deuterium, and R^E is H or D. In any of these embodiments, R² can be further substituted by deuterium, alkyl, and partially or fully deuterated alkyl.
In some embodiments, at least one of R¹ and R² is a substituted or unsubstituted group selected from the group consisting of phenyl, pyridine, pyrimidine, pyridazine, pyrazine, and triazine. In some such embodiments, R¹, R², or both can independently be further substituted by deuterium, alkyl, and partially or fully deuterated alkyl.
In some embodiments, R¹ is a substituted or unsubstituted group selected from the group consisting of phenyl, pyridine, pyrimidine, pyridazine, pyrazine, and triazine. In some such embodiments, R¹ can independently be further substituted by deuterium, alkyl, and partially or fully deuterated alkyl.
In some embodiments, R² is a substituted or unsubstituted group selected from the group consisting of phenyl, pyridine, pyrimidine, pyridazine, pyrazine, and triazine. In some such embodiments, R² can be further substituted by deuterium, alkyl, and partially or fully deuterated alkyl.
In some embodiments, each of R¹ and R² is independently a substituted or unsubstituted group selected from the group consisting of phenyl, pyridine, pyrimidine, pyridazine, pyrazine, and triazine. In some such embodiments, R¹, R², or both can independently be further substituted by deuterium, alkyl, and partially or fully deuterated alkyl.
In some embodiments, R¹ and R² together comprise a total of 6 or more carbon atoms. In some embodiments, R¹ and R² together comprise from 6 to 21 carbon atoms.
In some embodiments, at least one of R¹ and R² is a para-substituted 6-membered ring. In some such embodiments, the para-substitution comprises at least 3 carbon atoms. In some such embodiments, the para-substitution comprises at least 4 carbon atoms, or at least 5 carbon atoms, or at least 6 carbon atoms, or at least 7 carbon atoms, or at least 8 carbon atoms, or at least 9 carbon atoms, or at least 10 carbon atoms, or at least 11 carbon atoms, or at least 12 carbon atoms, or at least 13 carbon atoms, or at least 14 carbon atoms, or at least 15 carbon atoms.
In some embodiments, each of R¹ and R² can independently be further substituted by a moiety selected from the group consisting of the structures in the following LIST 1:
In some embodiments, at least one R^A is deuterium, alkyl, or a combination of both.
In some embodiments, at least one R^B is deuterium, alkyl, or a combination of both.
In some embodiments, at least one R^C is deuterium, alkyl, or a combination of both.
In some embodiments, at least one R^D is deuterium, alkyl, or a combination of both.
In some embodiments, at least one R^E is deuterium, alkyl, or a combination of both.
In some embodiments, moiety D is a polycyclic fused ring structure.
In some embodiments, moiety D is a polycyclic fused ring structure comprising at least three fused rings In some embodiments, the polycyclic fused ring structure has two 6-membered rings and one 5-membered ring. In some such embodiments, the 5-membered ring is fused to the ring coordinated to Ir and the second 6-membered ring is fused to the 5-membered ring. In some embodiments, moiety D is selected from the group consisting of dibenzofuran, dibenzothiophene, dibenzoselenophene, and aza-variants thereof. In some such embodiments, moiety D can be further substituted at the ortho- or meta-position of the O, S, or Se atom by a substituent selected from the group consisting of deuterium, fluorine, nitrile, alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof. In some such embodiments, the aza-variants contain exact one N atom at the 6-position (ortho to the O, S, or Se) with a substituent at the 7-position (meta to the O, S, or Se).
In some embodiments, moiety D is a polycyclic fused ring structure comprising at least four fused rings. In some embodiments, the polycyclic fused ring structure comprises three 6-membered rings and one 5-membered ring. In some such embodiments, the 5-membered ring is fused to the ring coordinated to Ir, the second 6-membered ring is fused to the 5-membered ring, and the third 6-membered ring is fused to the second 6-membered ring. In some such embodiments, the third 6-membered ring is further substituted by a substituent selected from the group consisting of deuterium, fluorine, nitrile, alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof.
In some embodiments, moiety D is a polycyclic fused ring structure comprising at least five fused rings. In some embodiments, the polycyclic fused ring structure comprises four 6-membered rings and one 5-membered ring or three 6-membered rings and two 5-membered rings. In some embodiments comprising two 5-membered rings, the 5-membered rings are fused together. In some embodiments comprising two 5-membered rings, the 5-membered rings are separated by at least one 6-membered ring. In some embodiments with one 5-membered ring, the 5-membered ring is fused to the ring coordinated to Ir, the second 6-membered ring is fused to the 5-membered ring, the third 6-membered ring is fused to the second 6-membered ring, and the fourth 6-membered ring is fused to the third-6-membered ring.
In some embodiments, moiety A is pyridine.
In some embodiments, moiety A is imidazole or benzimidazole. In some such embodiments, the N of the imidazole moiety not coordinated to Ir is substituted by aryl, aryl-substituted aryl, or alkyl-substituted aryl, which can be partially or fully deuterated. In some such embodiments, the substitution is on the one or both of the ortho positions of the carbon atom which is attached to the N of the imidazole moiety not coordinated to Ir.
In some embodiments, moiety C comprises a 5-membered ring. In some such embodiments, moiety C is selected from the group consisting of thiophene, benzothiophene, furan, benzofuran, and dibenzofuran.
In some embodiments, the ligand L_A is selected from the group consisting of:

wherein:

Xa is selected from the group consisting of O, S, NR, CR'R", and SiR'R";
Xb is selected from the group consisting of O, S, and NR; and
each of R, R', and R" is independently hydrogen or a substituent selected from the group consisting of the General Substituents defined herein.

In some embodiments, ligand L_A is selected from L_Ai, wherein i is an integer from 1 to 79, and each L_Ai is defined by the structures of the following LIST 2:

and

In some embodiments, ligand L_B is selected from the group consisting of L_B1-1 to L_B399-39 that follow the naming convention L_Bk-h, wherein k is an integer from 1 to 399, and h is an integer from 1 to 39; and wherein each of L_Bk-1 to L_Bk-39 is defined by the structure in the following LIST 3:

L_Bk-1 has the following structure	L_Bk-2 has the following structure	L_Bk-3 has the following structure

L_Bk-4 has the following structure	L_Bk-5 has the following structure	L_Bk-6 has the following structure

L_Bk-7 has the following structure	L_Bk-8 has the following structure	L_Bk-9 has the following structure

L_Bk-10 has the following structure	L_Bk-11 has the following structure	L_Bk-12 has the following structure

L_Bk-13 has the following structure	L_Bk-14 has the following structure	L_Bk-15 has the following structure

L_Bk-16 has the following structure	L_Bk-17 has the following structure	L_Bk-18 has the following structure

L_Bk-19 has the following structure	L_Bk-20 has the following structure	L_Bk-21 has the following structure

L_Bk-22 has the following structure	L_Bk-23 has the following structure	L_Bk-24 has the following structure

L_Bk-25 has the following structure	L_Bk-26 has the following structure	L_Bk-27 has the following structure

L_Bk-28 has the following structure	L_Bk-29 has the following structure	L_Bk-30 has the following structure

L_Bk-31 has the following structure	, L_Bk-32 has the following structure	L_Bk-33 has the following structure

L_Bk-34 has the following structure	, L_Bk-35 has the following structure	L_Bk-36 has the following structure

L_Bk-37 has the following structure	, L_Bk-38 has the following structure	L_Bk-39 has the following structure

wherein, for each k, R^F and R^G are defined in the following LIST 4:

k	R^F	R^G	k	R^F	R^G	k	R^F	R^G
1	R¹	R¹	134	R²⁶	R¹	267	R³⁰	R¹
2	R¹	R²	135	R²⁶	R²	268	R³⁰	R²
3	R¹	R³	136	R²⁶	R³	269	R³⁰	R³
4	R¹	R⁴	137	R²⁶	R⁴	270	R³⁰	R⁴
5	R¹	R⁵	138	R²⁶	R⁵	271	R³⁰	R⁵
6	R¹	R⁶	139	R²⁶	R⁶	272	R³⁰	R⁶
7	R¹	R⁷	140	R²⁶	R⁷	273	R³⁰	R⁷
8	R¹	R⁸	141	R²⁶	R⁸	274	R³⁰	R⁸
9	R¹	R⁹	142	R²⁶	R⁹	275	R³⁰	R⁹
10	R¹	R¹⁰	143	R²⁶	R¹⁰	276	R³⁰	R¹⁰
11	R¹	R¹¹	144	R²⁶	R¹¹	277	R³⁰	R¹¹
12	R¹	R¹²	145	R²⁶	R¹²	278	R³⁰	R¹²
13	R¹	R¹³	146	R²⁶	R¹³	279	R³⁰	R¹³
14	R¹	R¹⁴	147	R²⁶	R¹⁴	280	R³⁰	R¹⁴
15	R¹	R¹⁵	148	R²⁶	R¹⁵	281	R³⁰	R¹⁵
16	R¹	R¹⁶	149	R²⁶	R¹⁶	282	R³⁰	R¹⁶
17	R¹	R¹⁷	150	R²⁶	R¹⁷	283	R³⁰	R¹⁷
18	R¹	R¹⁸	151	R²⁶	R¹⁸	284	R³⁰	R¹⁸
19	R¹	R¹⁹	152	R²⁶	R¹⁹	285	R³⁰	R¹⁹
20	R¹	R²⁰	153	R²⁶	R²⁰	286	R³⁰	R²⁰
21	R¹	R²¹	154	R²⁶	R²¹	287	R³⁰	R²¹
22	R¹	R²²	155	R²⁶	R²²	288	R³⁰	R²²
23	R¹	R²³	156	R²⁶	R²³	289	R³⁰	R²³
24	R¹	R²⁴	157	R²⁶	R²⁴	290	R³⁰	R²⁴
25	R¹	R²⁵	158	R²⁶	R²⁵	291	R³⁰	R²⁵
26	R¹	R²⁶	159	R²⁶	R²⁶	292	R³⁰	R²⁶
27	R¹	R²⁷	160	R²⁶	R²⁷	293	R³⁰	R²⁷
28	R¹	R²⁸	161	R²⁶	R²⁸	294	R³⁰	R²⁸
29	R¹	R²⁹	162	R²⁶	R²⁹	295	R³⁰	R²⁹
30	R¹	R³⁰	163	R²⁶	R³⁰	296	R³⁰	R³⁰
31	R¹	R³¹	164	R²⁶	R³¹	297	R³⁰	R³¹
32	R¹	R³²	165	R²⁶	R³²	298	R³⁰	R³²
33	R¹	R³³	166	R²⁶	R³³	299	R³⁰	R³³
34	R¹	R³⁴	167	R²⁶	R³⁴	300	R³⁰	R³⁴
35	R¹	R³⁵	168	R²⁶	R³⁵	301	R³⁰	R³⁵
36	R¹	R³⁶	169	R²⁶	R³⁶	302	R³⁰	R³⁶
37	R¹	R³⁷	170	R²⁶	R³⁷	303	R³⁰	R³⁷
38	R¹	R³⁸	171	R²⁶	R³⁸	304	R³⁰	R³⁸
39	R¹	R³⁹	172	R²⁶	R³⁹	305	R³⁰	R³⁹
40	R¹	R⁴⁰	173	R²⁶	R⁴⁰	306	R³⁰	R⁴⁰
41	R¹	R⁴¹	174	R²⁶	R⁴¹	307	R³⁰	R⁴¹
42	R¹	R⁴²	175	R²⁶	R⁴²	308	R³⁰	R⁴²
43	R¹	R⁴³	176	R²⁶	R⁴³	309	R³⁰	R⁴³
44	R¹	R⁴⁴	177	R²⁶	R⁴⁴	310	R³⁰	R⁴⁴
45	R¹	R⁴⁵	178	R²⁶	R⁴⁵	311	R³⁰	R⁴⁵
46	R¹	R⁴⁶	179	R²⁶	R⁴⁶	312	R³⁰	R⁴⁶
47	R¹	R⁴⁷	180	R²⁶	R⁴⁷	313	R³⁰	R⁴⁷
48	R¹	R⁴⁸	181	R²⁶	R⁴⁸	314	R³⁰	R⁴⁸
49	R¹	R⁴⁹	182	R²⁶	R⁴⁹	315	R³⁰	R⁴⁹
50	R¹	R⁵⁰	183	R²⁶	R⁵⁰	316	R³⁰	R⁵⁰
51	R¹	R⁵¹	184	R²⁶	R⁵¹	317	R³⁰	R⁵¹
52	R¹	R⁵²	185	R²⁶	R⁵²	318	R³⁰	R⁵²
53	R¹	R⁵³	186	R²⁶	R⁵³	319	R³⁰	R⁵³
54	R¹	R⁵⁴	187	R²⁶	R⁵⁴	320	R³⁰	R⁵⁴
55	R¹	R⁵⁵	188	R²⁶	R⁵⁵	321	R³⁰	R⁵⁵
56	R¹	R⁵⁶	189	R²⁶	R⁵⁶	322	R³⁰	R⁵⁶
57	R¹	R⁵⁷	190	R²⁶	R⁵⁷	323	R³⁰	R⁵⁷
58	R¹	R⁵⁸	191	R²⁶	R⁵⁸	324	R³⁰	R⁵⁸
59	R¹	R⁵⁹	192	R²⁶	R⁵⁹	325	R³⁰	R⁵⁹
60	R¹	R⁶⁰	193	R²⁶	R⁶⁰	326	R³⁰	R⁶⁰
61	R¹	R⁶¹	194	R²⁶	R⁶¹	327	R³⁰	R⁶¹
62	R¹	R⁶²	195	R²⁶	R⁶²	328	R³⁰	R⁶²
63	R¹	R⁶³	196	R²⁶	R⁶³	329	R³⁰	R⁶³
64	R¹	R⁶⁴	197	R²⁶	R⁶⁴	330	R³⁰	R⁶⁴
65	R¹	R⁶⁵	198	R²⁶	R⁶⁵	331	R³⁰	R⁶⁵
66	R¹	R⁶⁶	199	R²⁶	R⁶⁶	332	R³⁰	R⁶⁶
67	R¹	R⁶⁷	200	R²⁶	R⁶⁷	333	R³⁰	R⁶⁷
68	R²	R¹	201	R¹	R²⁶	334	R¹	R³⁰
69	R³	R¹	202	R²	R²⁶	335	R²	R³⁰
70	R⁴	R¹	203	R³	R²⁶	336	R³	R³⁰
71	R⁵	R¹	204	R⁴	R²⁶	337	R⁴	R³⁰
72	R⁶	R¹	205	R⁵	R²⁶	338	R⁵	R³⁰
73	R⁷	R¹	206	R⁶	R²⁶	339	R⁶	R³⁰
74	R⁸	R¹	207	R⁷	R²⁶	340	R⁷	R³⁰
75	R⁹	R¹	208	R⁸	R²⁶	341	R⁸	R³⁰
76	R¹⁰	R¹	209	R⁹	R²⁶	342	R⁹	R³⁰
77	R¹¹	R¹	210	R¹⁰	R²⁶	343	R¹⁰	R³⁰
78	R¹²	R¹	211	R¹¹	R²⁶	344	R¹¹	R³⁰
79	R¹³	R¹	212	R¹²	R²⁶	345	R¹²	R³⁰
80	R¹⁴	R¹	213	R¹³	R²⁶	346	R¹³	R³⁰
81	R¹⁵	R¹	214	R¹⁴	R²⁶	347	R¹⁴	R³⁰
82	R¹⁶	R¹	215	R¹⁵	R²⁶	348	R¹⁵	R³⁰
83	R¹⁷	R¹	216	R¹⁶	R²⁶	349	R¹⁶	R³⁰
84	R¹⁸	R¹	217	R¹⁷	R²⁶	350	R¹⁷	R³⁰
85	R¹⁹	R¹	218	R¹⁸	R²⁶	351	R¹⁸	R³⁰
86	R²⁰	R¹	219	R¹⁹	R²⁶	352	R¹⁹	R³⁰
87	R²¹	R¹	220	R²⁰	R²⁶	353	R²⁰	R³⁰
88	R²²	R¹	221	R²¹	R²⁶	354	R²¹	R³⁰
89	R²³	R¹	222	R²²	R²⁶	355	R²²	R³⁰
90	R²⁴	R¹	223	R²³	R²⁶	356	R²³	R³⁰
91	R²⁵	R¹	224	R²⁴	R²⁶	357	R²⁴	R³⁰
92	R²⁶	R¹	225	R²⁵	R²⁶	358	R²⁵	R³⁰
93	R²⁷	R¹	226	R²⁷	R²⁶	359	R²⁶	R³⁰
94	R²⁸	R¹	227	R²⁸	R²⁶	360	R²⁷	R³⁰
95	R²⁹	R¹	228	R²⁹	R²⁶	361	R²⁸	R³⁰
96	R³⁰	R¹	229	R³⁰	R²⁶	362	R²⁹	R³⁰
97	R³¹	R¹	230	R³¹	R²⁶	363	R³¹	R³⁰
98	R³²	R¹	231	R³²	R²⁶	364	R³²	R³⁰
99	R³³	R¹	232	R³³	R²⁶	365	R³³	R³⁰
100	R³⁴	R¹	233	R³⁴	R²⁶	366	R³⁴	R³⁰
101	R³⁵	R¹	234	R³⁵	R²⁶	367	R³⁵	R³⁰
102	R³⁶	R¹	235	R³⁶	R²⁶	368	R³⁶	R³⁰
103	R³⁷	R¹	236	R³⁷	R²⁶	369	R³⁷	R³⁰
104	R³⁸	R¹	237	R³⁸	R²⁶	370	R³⁸	R³⁰
105	R³⁹	R¹	238	R³⁹	R²⁶	371	R³⁹	R³⁰
106	R⁴⁰	R¹	239	R⁴⁰	R²⁶	372	R⁴⁰	R³⁰
107	R⁴¹	R¹	240	R⁴¹	R²⁶	373	R⁴¹	R³⁰
108	R⁴²	R¹	241	R⁴²	R²⁶	374	R⁴²	R³⁰
109	R⁴³	R¹	242	R⁴³	R²⁶	375	R⁴³	R³⁰
110	R⁴⁴	R¹	243	R⁴⁴	R²⁶	376	R⁴⁴	R³⁰
111	R⁴⁵	R¹	244	R⁴⁵	R²⁶	377	R⁴⁵	R³⁰
112	R⁴⁶	R¹	245	R⁴⁶	R²⁶	378	R⁴⁶	R³⁰
113	R⁴⁷	R¹	246	R⁴⁷	R²⁶	379	R⁴⁷	R³⁰
114	R⁴⁸	R¹	247	R⁴⁸	R²⁶	380	R⁴⁸	R³⁰
115	R⁴⁹	R¹	248	R⁴⁹	R²⁶	381	R⁴⁹	R³⁰
116	R⁵⁰	R¹	249	R⁵⁰	R²⁶	382	R⁵⁰	R³⁰
117	R⁵¹	R¹	250	R⁵¹	R²⁶	383	R⁵¹	R³⁰
118	R⁵²	R¹	251	R⁵²	R²⁶	384	R⁵²	R³⁰
119	R⁵³	R¹	252	R⁵³	R²⁶	385	R⁵³	R³⁰
120	R⁵⁴	R¹	253	R⁵⁴	R²⁶	386	R⁵⁴	R³⁰
121	R⁵⁵	R¹	254	R⁵⁵	R²⁶	387	R⁵⁵	R³⁰
122	R⁵⁶	R¹	255	R⁵⁶	R²⁶	388	R⁵⁶	R³⁰
123	R⁵⁷	R¹	256	R⁵⁷	R²⁶	389	R⁵⁷	R³⁰
124	R⁵⁸	R¹	257	R⁵⁸	R²⁶	390	R⁵⁸	R³⁰
125	R⁵⁹	R¹	258	R⁵⁹	R²⁶	391	R⁵⁹	R³⁰
126	R⁶⁰	R¹	259	R⁶⁰	R²⁶	392	R⁶⁰	R³⁰
127	R⁶¹	R¹	260	R⁶¹	R²⁶	393	R⁶¹	R³⁰
128	R⁶²	R¹	261	R⁶²	R²⁶	394	R⁶²	R³⁰
129	R⁶³	R¹	262	R⁶³	R²⁶	395	R⁶³	R³⁰
130	R⁶⁴	R¹	263	R⁶⁴	R²⁶	396	R⁶⁴	R³⁰
131	R⁶⁵	R¹	264	R⁶⁵	R²⁶	397	R⁶⁵	R³⁰
132	R⁶⁶	R¹	265	R⁶⁶	R²⁶	398	R⁶⁶	R³⁰
133	R⁶⁷	R¹	266	R⁶⁷	R²⁶	399	R⁶⁷	R³⁰

wherein R¹ to R⁶⁷ have the structures in the following LIST 5:

In some embodiments, the compound has a Formula Ir(L_Ai)(L_Bk-h)₂, or a Formula Ir(L_Ai)₂(L_Bk-h), wherein i is an integer from 1 to 79, and k is an integer from 1 to 399, and h is an integer from 1 to 39; and each structure of L_Ai and L_Bk-h is as defined herein.
In some embodiments, the compound is selected from the group consisting of the structures of the following LIST 6:

and
In another aspect, the compound is selected from the group consisting of:

and
In some embodiments, the compound having a structure of Formula I described herein can be at least 30% deuterated, at least 40% deuterated, at least 50% deuterated, at least 60% deuterated, at least 70% deuterated, at least 80% deuterated, at least 90% deuterated, at least 95% deuterated, at least 99% deuterated, or 100% deuterated. As used herein, percent deuteration has its ordinary meaning and includes the percent of possible hydrogen atoms (e.g., positions that are hydrogen, deuterium, or halogen) that are replaced by deuterium atoms.

C. The OLEDs and the Devices of the Present Disclosure

In another aspect, the present disclosure also provides an OLED device comprising a first organic layer that contains a compound as disclosed in the above compounds section of the present disclosure.
In some embodiments, the OLED comprises an anode, a cathode, and a first organic layer disposed between the anode and the cathode. The first organic layer can comprise a compound of Formula I as described herein.
In some embodiments, the organic layer may be an emissive layer and the compound as described herein may be an emissive dopant or a non-emissive dopant.
In some embodiments, the organic layer may further comprise a host, wherein the host comprises a triphenylene containing benzo-fused thiophene or benzo-fused furan, wherein any substituent in the host is an unfused substituent independently selected from the group consisting of C_nH_2n+1, OC_nH_2n+1, OAr₁, N(C_nH_2n+1)₂, N(Ar₁)(Ar₂), CH=CH-C_nH_2n+1, C=CC_nH_2n+1, Ar₁, Ar₁-Ar₂, C_nH_2n-Ar₁, or no substitution, wherein n is from 1 to 10; and wherein Ar₁ and Ar₂ are independently selected from the group consisting of benzene, biphenyl, naphthalene, triphenylene, carbazole, and heteroaromatic analogs thereof.
In some embodiments, the organic layer may further comprise a host, wherein host comprises at least one chemical group selected from the group consisting of triphenylene, carbazole, indolocarbazole, dibenzothiophene, dibenzofuran, dibenzoselenophene, 5λ2-benzo[d]benzo[4,5]imidazo[3,2-a]imidazole, 5,9-dioxa-13b-boranaphtho[3,2,1-de]anthracene, triazine, aza-triphenylene, aza-carbazole, aza-indolocarbazole, aza-dibenzothiophene, aza-dibenzofuran, aza-dibenzoselenophene, aza-5λ2-benzo[d]benzo[4,5]imidazo[3,2-a]imidazole, and aza-(5,9-dioxa-13b-boranaphtho[3,2,1-de]anthracene).
In some embodiments, the host may be selected from the HOST Group consisting of:

and combinations thereof.
In some embodiments, the organic layer may further comprise a host, wherein the host comprises a metal complex.
In some embodiments, the emissive layer can comprise two hosts, a first host and a second host. In some embodiments, the first host is a hole transporting host, and the second host is an electron transporting host. In some embodiments, the first host and the second host can form an exciplex.
In some embodiments, the compound as described herein may be a sensitizer; wherein the device may further comprise an acceptor; and wherein the acceptor may be selected from the group consisting of fluorescent emitter, delayed fluorescence emitter, and combination thereof.
In yet another aspect, the OLED of the present disclosure may also comprise an emissive region containing a compound as disclosed in the above compounds section of the present disclosure.
In some embodiments, the emissive region can comprise a compound of Formula I as described herein.
In some embodiments, at least one of the anode, the cathode, or a new layer disposed over the organic emissive layer functions as an enhancement layer. The enhancement layer comprises a plasmonic material exhibiting surface plasmon resonance that non-radiatively couples to the emitter material and transfers excited state energy from the emitter material to non-radiative mode of surface plasmon polariton. The enhancement layer is provided no more than a threshold distance away from the organic emissive layer, wherein the emitter material has a total non-radiative decay rate constant and a total radiative decay rate constant due to the presence of the enhancement layer and the threshold distance is where the total non-radiative decay rate constant is equal to the total radiative decay rate constant. In some embodiments, the OLED further comprises an outcoupling layer. In some embodiments, the outcoupling layer is disposed over the enhancement layer on the opposite side of the organic emissive layer. In some embodiments, the outcoupling layer is disposed on opposite side of the emissive layer from the enhancement layer but still outcouples energy from the surface plasmon mode of the enhancement layer. The outcoupling layer scatters the energy from the surface plasmon polaritons. In some embodiments this energy is scattered as photons to free space. In other embodiments, the energy is scattered from the surface plasmon mode into other modes of the device such as but not limited to the organic waveguide mode, the substrate mode, or another waveguiding mode. If energy is scattered to the non-free space mode of the OLED other outcoupling schemes could be incorporated to extract that energy to free space. In some embodiments, one or more intervening layer can be disposed between the enhancement layer and the outcoupling layer. The examples for interventing layer(s) can be dielectric materials, including organic, inorganic, perovskites, oxides, and may include stacks and/or mixtures of these materials.
The enhancement layer modifies the effective properties of the medium in which the emitter material resides resulting in any or all of the following: a decreased rate of emission, a modification of emission line-shape, a change in emission intensity with angle, a change in the stability of the emitter material, a change in the efficiency of the OLED, and reduced efficiency roll-off of the OLED device. Placement of the enhancement layer on the cathode side, anode side, or on both sides results in OLED devices which take advantage of any of the above-mentioned effects. In addition to the specific functional layers mentioned herein and illustrated in the various OLED examples shown in the figures, the OLEDs according to the present disclosure may include any of the other functional layers often found in OLEDs.
The enhancement layer can be comprised of plasmonic materials, optically active metamaterials, or hyperbolic metamaterials. As used herein, a plasmonic material is a material in which the real part of the dielectric constant crosses zero in the visible or ultraviolet region of the electromagnetic spectrum. In some embodiments, the plasmonic material includes at least one metal. In such embodiments the metal may include at least one of Ag, Al, Au, Ir, Pt, Ni, Cu, W, Ta, Fe, Cr, Mg, Ga, Rh, Ti, Ru, Pd, In, Bi, Ca alloys or mixtures of these materials, and stacks of these materials. In general, a metamaterial is a medium composed of different materials where the medium as a whole acts differently than the sum of its material parts. In particular, we define optically active metamaterials as materials which have both negative permittivity and negative permeability. Hyperbolic metamaterials, on the other hand, are anisotropic media in which the permittivity or permeability are of different sign for different spatial directions. Optically active metamaterials and hyperbolic metamaterials are strictly distinguished from many other photonic structures such as Distributed Bragg Reflectors ("DBRs") in that the medium should appear uniform in the direction of propagation on the length scale of the wavelength of light. Using terminology that one skilled in the art can understand: the dielectric constant of the metamaterials in the direction of propagation can be described with the effective medium approximation. Plasmonic materials and metamaterials provide methods for controlling the propagation of light that can enhance OLED performance in a number of ways.
In some embodiments, the enhancement layer is provided as a planar layer. In other embodiments, the enhancement layer has wavelength-sized features that are arranged periodically, quasi-periodically, or randomly, or sub-wavelength-sized features that are arranged periodically, quasi-periodically, or randomly. In some embodiments, the wavelength-sized features and the sub-wavelength-sized features have sharp edges.
In some embodiments, the outcoupling layer has wavelength-sized features that are arranged periodically, quasi-periodically, or randomly, or sub-wavelength-sized features that are arranged periodically, quasi-periodically, or randomly. In some embodiments, the outcoupling layer may be composed of a plurality of nanoparticles and in other embodiments the outcoupling layer is composed of a pluraility of nanoparticles disposed over a material. In these embodiments the outcoupling may be tunable by at least one of varying a size of the plurality of nanoparticles, varying a shape of the plurality of nanoparticles, changing a material of the plurality of nanoparticles, adjusting a thickness of the material, changing the refractive index of the material or an additional layer disposed on the plurality of nanoparticles, varying a thickness of the enhancement layer, and/or varying the material of the enhancement layer. The plurality of nanoparticles of the device may be formed from at least one of metal, dielectric material, semiconductor materials, an alloy of metal, a mixture of dielectric materials, a stack or layering of one or more materials, and/or a core of one type of material and that is coated with a shell of a different type of material. In some embodiments, the outcoupling layer is composed of at least metal nanoparticles wherein the metal is selected from the group consisting of Ag, Al, Au, Ir, Pt, Ni, Cu, W, Ta, Fe, Cr, Mg, Ga, Rh, Ti, Ru, Pd, In, Bi, Ca, alloys or mixtures of these materials, and stacks of these materials. The plurality of nanoparticles may have additional layer disposed over them. In some embodiments, the polarization of the emission can be tuned using the outcoupling layer. Varying the dimensionality and periodicity of the outcoupling layer can select a type of polarization that is preferentially outcoupled to air. In some embodiments the outcoupling layer also acts as an electrode of the device.
In yet another aspect, the present disclosure also provides a consumer product comprising an organic light-emitting device (OLED) having an anode; a cathode; and an organic layer disposed between the anode and the cathode, wherein the organic layer may comprise a compound as disclosed in the above compounds section of the present disclosure.
In some embodiments, the consumer product comprises an OLED having an anode; a cathode; and an organic layer disposed between the anode and the cathode, wherein the organic layer can comprise a compound of Formula I as described herein.
In some embodiments, the consumer product can be one of a flat panel display, a computer monitor, a medical monitor, a television, a billboard, a light for interior or exterior illumination and/or signaling, a heads-up display, a fully or partially transparent display, a flexible display, a laser printer, a telephone, a cell phone, tablet, a phablet, a personal digital assistant (PDA), a wearable device, a laptop computer, a digital camera, a camcorder, a viewfinder, a micro-display that is less than 2 inches diagonal, a 3-D display, a virtual reality or augmented reality display, a vehicle, a video wall comprising multiple displays tiled together, a theater or stadium screen, a light therapy device, and a sign.
Generally, an OLED comprises at least one organic layer disposed between and electrically connected to an anode and a cathode. When a current is applied, the anode injects holes and the cathode injects electrons into the organic layer(s). The injected holes and electrons each migrate toward the oppositely charged electrode. When an electron and hole localize on the same molecule, an "exciton," which is a localized electron-hole pair having an excited energy state, is formed. Light is emitted when the exciton relaxes via a photoemissive mechanism. In some cases, the exciton may be localized on an excimer or an exciplex. Non-radiative mechanisms, such as thermal relaxation, may also occur, but are generally considered undesirable.
Several OLED materials and configurations are described in U.S. Pat. Nos. 5,844,363 , 6,303,238 , and 5,707,745 , which are incorporated herein by reference in their entirety.
The initial OLEDs used emissive molecules that emitted light from their singlet states ("fluorescence") as disclosed, for example, in U.S. Pat. No. 4,769,292 , which is incorporated by reference in its entirety. Fluorescent emission generally occurs in a time frame of less than 10 nanoseconds.
More recently, OLEDs having emissive materials that emit light from triplet states ("phosphorescence") have been demonstrated. Baldo et al., "Highly Efficient Phosphorescent Emission from Organic Electroluminescent Devices," Nature, vol. 395, 151-154, 1998; ("Baldo-I") and Baldo et al., "Very high-efficiency green organic light-emitting devices based on electrophosphorescence," Appl. Phys. Lett., vol. 75, No. 3, 4-6 (1999) ("Baldo-II"), are incorporated by reference in their entireties. Phosphorescence is described in more detail in U.S. Pat. No. 7,279,704 at cols. 5-6, which are incorporated by reference.
FIG. 1 shows an organic light emitting device 100. The figures are not necessarily drawn to scale. Device 100 may include a substrate 110, an anode 115, a hole injection layer 120, a hole transport layer 125, an electron blocking layer 130, an emissive layer 135, a hole blocking layer 140, an electron transport layer 145, an electron injection layer 150, a protective layer 155, a cathode 160, and a barrier layer 170. Cathode 160 is a compound cathode having a first conductive layer 162 and a second conductive layer 164. Device 100 may be fabricated by depositing the layers described, in order. The properties and functions of these various layers, as well as example materials, are described in more detail in US 7,279,704 at cols. 6-10, which are incorporated by reference.
More examples for each of these layers are available. For example, a flexible and transparent substrate-anode combination is disclosed in U.S. Pat. No. 5,844,363 , which is incorporated by reference in its entirety. An example of a p-doped hole transport layer is m-MTDATA doped with F₄-TCNQ at a molar ratio of 50:1, as disclosed in U.S. Patent Application Publication No. 2003/0230980 , which is incorporated by reference in its entirety. Examples of emissive and host materials are disclosed in U.S. Pat. No. 6,303,238 to Thompson et al. , which is incorporated by reference in its entirety. An example of an n-doped electron transport layer is BPhen doped with Li at a molar ratio of 1:1, as disclosed in U.S. Patent Application Publication No. 2003/0230980 , which is incorporated by reference in its entirety. U.S. Pat. Nos. 5,703,436 and 5,707,745 , which are incorporated by reference in their entireties, disclose examples of cathodes including compound cathodes having a thin layer of metal such as Mg:Ag with an overlying transparent, electrically-conductive, sputter-deposited ITO layer. The theory and use of blocking layers is described in more detail in U.S. Pat. No. 6,097,147 and U.S. Patent Application Publication No. 2003/0230980 , which are incorporated by reference in their entireties. Examples of injection layers are provided in U.S. Patent Application Publication No. 2004/0174116 , which is incorporated by reference in its entirety. A description of protective layers may be found in U.S. Patent Application Publication No. 2004/0174116 , which is incorporated by reference in its entirety.
FIG. 2 shows an inverted OLED 200. The device includes a substrate 210, a cathode 215, an emissive layer 220, a hole transport layer 225, and an anode 230. Device 200 may be fabricated by depositing the layers described, in order. Because the most common OLED configuration has a cathode disposed over the anode, and device 200 has cathode 215 disposed under anode 230, device 200 may be referred to as an "inverted" OLED. Materials similar to those described with respect to device 100 may be used in the corresponding layers of device 200. FIG. 2 provides one example of how some layers may be omitted from the structure of device 100.
The simple layered structure illustrated in FIGS. 1 and 2 is provided by way of non-limiting example, and it is understood that embodiments of the present disclosure may be used in connection with a wide variety of other structures. The specific materials and structures described are exemplary in nature, and other materials and structures may be used. Functional OLEDs may be achieved by combining the various layers described in different ways, or layers may be omitted entirely, based on design, performance, and cost factors. Other layers not specifically described may also be included. Materials other than those specifically described may be used. Although many of the examples provided herein describe various layers as comprising a single material, it is understood that combinations of materials, such as a mixture of host and dopant, or more generally a mixture, may be used. Also, the layers may have various sublayers. The names given to the various layers herein are not intended to be strictly limiting. For example, in device 200, hole transport layer 225 transports holes and injects holes into emissive layer 220, and may be described as a hole transport layer or a hole injection layer. In one embodiment, an OLED may be described as having an "organic layer" disposed between a cathode and an anode. This organic layer may comprise a single layer, or may further comprise multiple layers of different organic materials as described, for example, with respect to FIGS. 1 and 2.
Structures and materials not specifically described may also be used, such as OLEDs comprised of polymeric materials (PLEDs) such as disclosed in U.S. Pat. No. 5,247,190 to Friend et al. , which is incorporated by reference in its entirety. By way of further example, OLEDs having a single organic layer may be used. OLEDs may be stacked, for example as described in U.S. Pat. No. 5,707,745 to Forrest et al , which is incorporated by reference in its entirety. The OLED structure may deviate from the simple layered structure illustrated in FIGS. 1 and 2. For example, the substrate may include an angled reflective surface to improve outcoupling, such as a mesa structure as described in U.S. Pat. No. 6,091,195 to Forrest et al. , and/or a pit structure as described in U.S. Pat. No. 5,834,893 to Bulovic et al. , which are incorporated by reference in their entireties.
Unless otherwise specified, any of the layers of the various embodiments may be deposited by any suitable method. For the organic layers, preferred methods include thermal evaporation, ink-jet, such as described in U.S. Pat. Nos. 6,013,982 and 6,087,196 , which are incorporated by reference in their entireties, organic vapor phase deposition (OVPD), such as described in U.S. Pat. No. 6,337,102 to Forrest et al. , which is incorporated by reference in its entirety, and deposition by organic vapor jet printing (OVJP, also referred to as organic vapor jet deposition (OVJD)), such as described in U.S. Pat. No. 7,431,968 , which is incorporated by reference in its entirety. Other suitable deposition methods include spin coating and other solution based processes. Solution based processes are preferably carried out in nitrogen or an inert atmosphere. For the other layers, preferred methods include thermal evaporation. Preferred patterning methods include deposition through a mask, cold welding such as described in U.S. Pat. Nos. 6,294,398 and 6,468,819 , which are incorporated by reference in their entireties, and patterning associated with some of the deposition methods such as ink-jet and organic vapor jet printing (OVJP). Other methods may also be used. The materials to be deposited may be modified to make them compatible with a particular deposition method. For example, substituents such as alkyl and aryl groups, branched or unbranched, and preferably containing at least 3 carbons, may be used in small molecules to enhance their ability to undergo solution processing. Substituents having 20 carbons or more may be used, and 3-20 carbons are a preferred range. Materials with asymmetric structures may have better solution processability than those having symmetric structures, because asymmetric materials may have a lower tendency to recrystallize. Dendrimer substituents may be used to enhance the ability of small molecules to undergo solution processing.
Devices fabricated in accordance with embodiments of the present disclosure may further optionally comprise a barrier layer. One purpose of the barrier layer is to protect the electrodes and organic layers from damaging exposure to harmful species in the environment including moisture, vapor and/or gases, etc. The barrier layer may be deposited over, under or next to a substrate, an electrode, or over any other parts of a device including an edge. The barrier layer may comprise a single layer, or multiple layers. The barrier layer may be formed by various known chemical vapor deposition techniques and may include compositions having a single phase as well as compositions having multiple phases. Any suitable material or combination of materials may be used for the barrier layer. The barrier layer may incorporate an inorganic or an organic compound or both. The preferred barrier layer comprises a mixture of a polymeric material and a non-polymeric material as described in U.S. Pat. No. 7,968,146 , PCT Pat. Application Nos. PCT/US2007/023098 and PCT/US2009/042829 , which are herein incorporated by reference in their entireties. To be considered a "mixture", the aforesaid polymeric and non-polymeric materials comprising the barrier layer should be deposited under the same reaction conditions and/or at the same time. The weight ratio of polymeric to non-polymeric material may be in the range of 95:5 to 5:95. The polymeric material and the non-polymeric material may be created from the same precursor material. In one example, the mixture of a polymeric material and a non-polymeric material consists essentially of polymeric silicon and inorganic silicon.
Devices fabricated in accordance with embodiments of the present disclosure can be incorporated into a wide variety of electronic component modules (or units) that can be incorporated into a variety of electronic products or intermediate components. Examples of such electronic products or intermediate components include display screens, lighting devices such as discrete light source devices or lighting panels, etc. that can be utilized by the end-user product manufacturers. Such electronic component modules can optionally include the driving electronics and/or power source(s). Devices fabricated in accordance with embodiments of the present disclosure can be incorporated into a wide variety of consumer products that have one or more of the electronic component modules (or units) incorporated therein. A consumer product comprising an OLED that includes the compound of the present disclosure in the organic layer in the OLED is disclosed. Such consumer products would include any kind of products that include one or more light source(s) and/or one or more of some type of visual displays. Some examples of such consumer products include flat panel displays, curved displays, computer monitors, medical monitors, televisions, billboards, lights for interior or exterior illumination and/or signaling, heads-up displays, fully or partially transparent displays, flexible displays, rollable displays, foldable displays, stretchable displays, laser printers, telephones, mobile phones, tablets, phablets, personal digital assistants (PDAs), wearable devices, laptop computers, digital cameras, camcorders, viewfinders, micro-displays (displays that are less than 2 inches diagonal), 3-D displays, virtual reality or augmented reality displays, vehicles, video walls comprising multiple displays tiled together, theater or stadium screen, a light therapy device, and a sign. Various control mechanisms may be used to control devices fabricated in accordance with the present disclosure, including passive matrix and active matrix. Many of the devices are intended for use in a temperature range comfortable to humans, such as 18 degrees C. to 30 degrees C., and more preferably at room temperature (20-25 °C), but could be used outside this temperature range, for example, from -40 degree C to + 80 °C.
More details on OLEDs, and the definitions described above, can be found in U.S. Pat. No. 7,279,704 , which is incorporated herein by reference in its entirety.
The materials and structures described herein may have applications in devices other than OLEDs. For example, other optoelectronic devices such as organic solar cells and organic photodetectors may employ the materials and structures. More generally, organic devices, such as organic transistors, may employ the materials and structures.
In some embodiments, the OLED has one or more characteristics selected from the group consisting of being flexible, being rollable, being foldable, being stretchable, and being curved. In some embodiments, the OLED is transparent or semi-transparent. In some embodiments, the OLED further comprises a layer comprising carbon nanotubes.
In some embodiments, the OLED further comprises a layer comprising a delayed fluorescent emitter. In some embodiments, the OLED comprises a RGB pixel arrangement or white plus color filter pixel arrangement. In some embodiments, the OLED is a mobile device, a hand held device, or a wearable device. In some embodiments, the OLED is a display panel having less than 10 inch diagonal or 50 square inch area. In some embodiments, the OLED is a display panel having at least 10 inch diagonal or 50 square inch area. In some embodiments, the OLED is a lighting panel.
In some embodiments, the compound can be an emissive dopant. In some embodiments, the compound can produce emissions via phosphorescence, fluorescence, thermally activated delayed fluorescence, i.e., TADF (also referred to as E-type delayed fluorescence; see, e.g., U.S. Application No. 15/700,352 , which is hereby incorporated by reference in its entirety), triplet-triplet annihilation, or combinations of these processes. In some embodiments, the emissive dopant can be a racemic mixture, or can be enriched in one enantiomer. In some embodiments, the compound can be homoleptic (each ligand is the same). In some embodiments, the compound can be heteroleptic (at least one ligand is different from others). When there are more than one ligand coordinated to a metal, the ligands can all be the same in some embodiments. In some other embodiments, at least one ligand is different from the other ligands. In some embodiments, every ligand can be different from each other. This is also true in embodiments where a ligand being coordinated to a metal can be linked with other ligands being coordinated to that metal to form a tridentate, tetradentate, pentadentate, or hexadentate ligands. Thus, where the coordinating ligands are being linked together, all of the ligands can be the same in some embodiments, and at least one of the ligands being linked can be different from the other ligand(s) in some other embodiments.
In some embodiments, the compound can be used as a phosphorescent sensitizer in an OLED where one or multiple layers in the OLED contains an acceptor in the form of one or more fluorescent and/or delayed fluorescence emitters. In some embodiments, the compound can be used as one component of an exciplex to be used as a sensitizer. As a phosphorescent sensitizer, the compound must be capable of energy transfer to the acceptor and the acceptor will emit the energy or further transfer energy to a final emitter. The acceptor concentrations can range from 0.001% to 100%. The acceptor could be in either the same layer as the phosphorescent sensitizer or in one or more different layers. In some embodiments, the acceptor is a TADF emitter. In some embodiments, the acceptor is a fluorescent emitter. In some embodiments, the emission can arise from any or all of the sensitizer, acceptor, and final emitter.
According to another aspect, a formulation comprising the compound described herein is also disclosed.
The OLED disclosed herein can be incorporated into one or more of a consumer product, an electronic component module, and a lighting panel. The organic layer can be an emissive layer and the compound can be an emissive dopant in some embodiments, while the compound can be a non-emissive dopant in other embodiments.
In yet another aspect of the present disclosure, a formulation that comprises the novel compound disclosed herein is described. The formulation can include one or more components selected from the group consisting of a solvent, a host, a hole injection material, hole transport material, electron blocking material, hole blocking material, and an electron transport material, disclosed herein.
The present disclosure encompasses any chemical structure comprising the novel compound of the present disclosure, or a monovalent or polyvalent variant thereof. In other words, the inventive compound, or a monovalent or polyvalent variant thereof, can be a part of a larger chemical structure. Such chemical structure can be selected from the group consisting of a monomer, a polymer, a macromolecule, and a supramolecule (also known as supermolecule). As used herein, a "monovalent variant of a compound" refers to a moiety that is identical to the compound except that one hydrogen has been removed and replaced with a bond to the rest of the chemical structure. As used herein, a "polyvalent variant of a compound" refers to a moiety that is identical to the compound except that more than one hydrogen has been removed and replaced with a bond or bonds to the rest of the chemical structure. In the instance of a supramolecule, the inventive compound can also be incorporated into the supramolecule complex without covalent bonds.

D. Combination of the Compounds of the Present Disclosure with Other Materials

The materials described herein as useful for a particular layer in an organic light emitting device may be used in combination with a wide variety of other materials present in the device. For example, emissive dopants disclosed herein may be used in conjunction with a wide variety of hosts, transport layers, blocking layers, injection layers, electrodes and other layers that may be present. The materials described or referred to below are non-limiting examples of materials that may be useful in combination with the compounds disclosed herein, and one of skill in the art can readily consult the literature to identify other materials that may be useful in combination.

a) Conductivity Dopants:

A charge transport layer can be doped with conductivity dopants to substantially alter its density of charge carriers, which will in turn alter its conductivity. The conductivity is increased by generating charge carriers in the matrix material, and depending on the type of dopant, a change in the Fermi level of the semiconductor may also be achieved. Hole-transporting layer can be doped by p-type conductivity dopants and n-type conductivity dopants are used in the electron-transporting layer.
Non-limiting examples of the conductivity dopants that may be used in an OLED in combination with materials disclosed herein are exemplified below together with references that disclose those materials: EP01617493 , EP01968131 , EP2020694 , EP2684932 , US20050139810 , US20070160905 , US20090167167 , US2010288362 , WO06081780 , WO2009003455 , WO2009008277 , WO2009011327 , WO2014009310 , US2007252140 , US2015060804 , US20150123047 , and US2012146012 .

b) HIL/HTL:

A hole injecting/transporting material to be used in the present disclosure is not particularly limited, and any compound may be used as long as the compound is typically used as a hole injecting/transporting material. Examples of the material include, but are not limited to: a phthalocyanine or porphyrin derivative; an aromatic amine derivative; an indolocarbazole derivative; a polymer containing fluorohydrocarbon; a polymer with conductivity dopants; a conducting polymer, such as PEDOT/PSS; a self-assembly monomer derived from compounds such as phosphonic acid and silane derivatives; a metal oxide derivative, such as MoO_x; a p-type semiconducting organic compound, such as 1,4,5,8,9,12-Hexaazatriphenylenehexacarbonitrile; a metal complex, and a cross-linkable compounds.
Examples of aromatic amine derivatives used in HIL or HTL include, but not limit to the following general structures:
and
Each of Ar¹ to Ar⁹ is selected from the group consisting of aromatic hydrocarbon cyclic compounds such as benzene, biphenyl, triphenyl, triphenylene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene, chrysene, perylene, and azulene; the group consisting of aromatic heterocyclic compounds such as dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridylindole, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, indoxazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuropyridine, furodipyridine, benzothienopyridine, thienodipyridine, benzoselenophenopyridine, and selenophenodipyridine; and the group consisting of 2 to 10 cyclic structural units which are groups of the same type or different types selected from the aromatic hydrocarbon cyclic group and the aromatic heterocyclic group and are bonded to each other directly or via at least one of oxygen atom, nitrogen atom, sulfur atom, silicon atom, phosphorus atom, boron atom, chain structural unit and the aliphatic cyclic group. Each Ar may be unsubstituted or may be substituted by a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acids, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof.
In one aspect, Ar¹ to Ar⁹ is independently selected from the group consisting of:

wherein k is an integer from 1 to 20; X¹⁰¹ to X¹⁰⁸ is C (including CH) or N; Z¹⁰¹ is NAr¹, O, or S; Ar¹ has the same group defined above.
Examples of metal complexes used in HIL or HTL include, but are not limited to the following general formula:
wherein Met is a metal, which can have an atomic weight greater than 40; (Y¹⁰¹-Y¹⁰²) is a bidentate ligand, Y¹⁰¹ and Y¹⁰² are independently selected from C, N, O, P, and S; L¹⁰¹ is an ancillary ligand; k' is an integer value from 1 to the maximum number of ligands that may be attached to the metal; and k'+k" is the maximum number of ligands that may be attached to the metal.
In one aspect, (Y¹⁰¹-Y¹⁰²) is a 2-phenylpyridine derivative. In another aspect, (Y¹⁰¹-Y¹⁰²) is a carbene ligand. In another aspect, Met is selected from Ir, Pt, Os, and Zn. In a further aspect, the metal complex has a smallest oxidation potential in solution vs. Fc⁺/Fc couple less than about 0.6 V.
Non-limiting examples of the HIL and HTL materials that may be used in an OLED in combination with materials disclosed herein are exemplified below together with references that disclose those materials: CN102702075 , DE102012005215 , EP01624500 , EP01698613 , EP01806334 , EP01930964 , EP01972613 , EP01997799 , EP02011790 , EP02055700 , EP02055701 , EP1725079 , EP2085382 , EP2660300 , EP650955 , JP07-073529 , JP2005112765 , JP2007091719 , JP2008021687 , JP2014-009196 , KR20110088898 , KR20130077473 , TW201139402 , US06517957 , US20020158242 , US20030162053 , US20050123751 , US20060182993 , US20060240279 , US20070145888 , US20070181874 , US20070278938 , US20080014464 , US20080091025 , US20080106190 , US20080124572 , US20080145707 , US20080220265 , US20080233434 , US20080303417 , US2008107919 , US20090115320 , US20090167161 , US2009066235 , US2011007385 , US20110163302 , US2011240968 , US2011278551 , US2012205642 , US2013241401 , US20140117329 , US2014183517 , US5061569 , US5639914 , WO05075451 , WO07125714 , WO08023550 , WO08023759 , WO2009145016 , WO2010061824 , WO2011075644 , WO2012177006 , WO2013018530 , WO2013039073 , WO2013087142 , WO2013118812 , WO2013120577 , WO2013157367 , WO2013175747 , WO2014002873 , WO2014015935 , WO2014015937 , WO2014030872 , WO2014030921 , WO2014034791 , WO2014104514 , WO2014157018 .

and

c) EBL:

An electron blocking layer (EBL) may be used to reduce the number of electrons and/or excitons that leave the emissive layer. The presence of such a blocking layer in a device may result in substantially higher efficiencies, and/or longer lifetime, as compared to a similar device lacking a blocking layer. Also, a blocking layer may be used to confine emission to a desired region of an OLED. In some embodiments, the EBL material has a higher LUMO (closer to the vacuum level) and/or higher triplet energy than the emitter closest to the EBL interface. In some embodiments, the EBL material has a higher LUMO (closer to the vacuum level) and/or higher triplet energy than one or more of the hosts closest to the EBL interface. In one aspect, the compound used in EBL contains the same molecule or the same functional groups used as one of the hosts described below.

d) Hosts:

The light emitting layer of the organic EL device of the present disclosure preferably contains at least a metal complex as light emitting material, and may contain a host material using the metal complex as a dopant material. Examples of the host material are not particularly limited, and any metal complexes or organic compounds may be used as long as the triplet energy of the host is larger than that of the dopant. Any host material may be used with any dopant so long as the triplet criteria is satisfied.
Examples of metal complexes used as host are preferred to have the following general formula:
wherein Met is a metal; (Y¹⁰³-Y¹⁰⁴) is a bidentate ligand, Y¹⁰³ and Y¹⁰⁴ are independently selected from C, N, O, P, and S; L¹⁰¹ is an another ligand; k' is an integer value from 1 to the maximum number of ligands that may be attached to the metal; and k'+k" is the maximum number of ligands that may be attached to the metal.
In one aspect, the metal complexes are:
wherein (O-N) is a bidentate ligand, having metal coordinated to atoms O and N.
In another aspect, Met is selected from Ir and Pt. In a further aspect, (Y¹⁰³-Y¹⁰⁴) is a carbene ligand.
In one aspect, the host compound contains at least one of the following groups selected from the group consisting of aromatic hydrocarbon cyclic compounds such as benzene, biphenyl, triphenyl, triphenylene, tetraphenylene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene, chrysene, perylene, and azulene; the group consisting of aromatic heterocyclic compounds such as dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridylindole, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, indoxazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuropyridine, furodipyridine, benzothienopyridine, thienodipyridine, benzoselenophenopyridine, and selenophenodipyridine; and the group consisting of 2 to 10 cyclic structural units which are groups of the same type or different types selected from the aromatic hydrocarbon cyclic group and the aromatic heterocyclic group and are bonded to each other directly or via at least one of oxygen atom, nitrogen atom, sulfur atom, silicon atom, phosphorus atom, boron atom, chain structural unit and the aliphatic cyclic group. Each option within each group may be unsubstituted or may be substituted by a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acids, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof.
In one aspect, the host compound contains at least one of the following groups in the molecule:

wherein R¹⁰¹ is selected from the group consisting of hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acids, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof, and when it is aryl or heteroaryl, it has the similar definition as Ar's mentioned above. k is an integer from 0 to 20 or 1 to 20. X¹⁰¹ to X¹⁰⁸ are independently selected from C (including CH) or N. Z¹⁰¹ and Z¹⁰² are independently selected from NR¹⁰¹, O, or S.
Non-limiting examples of the host materials that may be used in an OLED in combination with materials disclosed herein are exemplified below together with references that disclose those materials: EP2034538 , EP2034538A , EP2757608 , JP2007254297 , KR20100079458 , KR20120088644 , KR20120129733 , KR20130115564 , TW201329200 , US20030175553 , US20050238919 , US20060280965 , US20090017330 , US20090030202 , US20090167162 , US20090302743 , US20090309488 , US20100012931 , US20100084966 , US20100187984 , US2010187984 , US2012075273 , US2012126221 , US2013009543 , US2013105787 , US2013175519 , US2014001446 , US20140183503 , US20140225088 , US2014034914 , US7154114 , WO2001039234 , WO2004093207 , WO2005014551 , WO2005089025 , WO2006072002 , WO2006114966 , WO2007063754 , WO2008056746 , WO2009003898 , WO2009021126 , WO2009063833 , WO2009066778 , WO2009066779 , WO2009086028 , WO2010056066 , WO2010107244 , WO2011081423 , WO2011081431 , WO2011086863 , WO2012128298 , WO2012133644 , WO2012133649 , WO2013024872 , WO2013035275 , WO2013081315 , WO2013191404 , WO2014142472 , US20170263869 , US20160163995 , US9466803 ,

e) Additional Emitters:

One or more additional emitter dopants may be used in conjunction with the compound of the present disclosure. Examples of the additional emitter dopants are not particularly limited, and any compounds may be used as long as the compounds are typically used as emitter materials. Examples of suitable emitter materials include, but are not limited to, compounds which can produce emissions via phosphorescence, fluorescence, thermally activated delayed fluorescence, i.e., TADF (also referred to as E-type delayed fluorescence), triplet-triplet annihilation, or combinations of these processes.
Non-limiting examples of the emitter materials that may be used in an OLED in combination with materials disclosed herein are exemplified below together with references that disclose those materials: CN103694277 , CN1696137 , EB01238981, EP01239526 , EP01961743 , EP1239526 , EP1244155 , EP1642951 , EP1647554 , EP1841834 , EP1841834B , EP2062907 , EP2730583 , JP2012074444 , JP2013110263 , JP4478555 , KR1020090133652 , KR20120032054 , KR20130043460 , TW201332980 , US06699599 , US06916554 , US20010019782 , US20020034656 , US20030068526 , US20030072964 , US20030138657 , US20050123788 , US20050244673 , US2005123791 , US2005260449 , US20060008670 , US20060065890 , US20060127696 , US20060134459 , US20060134462 , US20060202194 , US20060251923 , US20070034863 , US20070087321 , US20070103060 , US20070111026 , US20070190359 , US20070231600 , US2007034863 , US2007104979 , US2007104980 , US2007138437 , US2007224450 , US2007278936 , US20080020237 , US20080233410 , US20080261076 , US20080297033 , US200805851 , US2008161567 , US2008210930 , US20090039776 , US20090108737 , US20090115322 , US20090179555 , US2009085476 , US2009104472 , US20100090591 , US20100148663 , US20100244004 , US20100295032 , US2010102716 , US2010105902 , US2010244004 , US2010270916 , US20110057559 , US20110108822 , US20110204333 , US2011215710 , US2011227049 , US2011285275 , US2012292601 , US20130146848 , US2013033172 , US2013165653 , US2013181190 , US2013334521 , US20140246656 , US2014103305 , US6303238 , US6413656 , US6653654 , US6670645 , US6687266 , US6835469 , US6921915 , US7279704 , US7332232 , US7378162 , US7534505 , US7675228 , US7728137 , US7740957 , US7759489 , US7951947 , US8067099 , US8592586 , US8871361 , WO06081973 , WO06121811 , WO07018067 , WO07108362 , WO07115970 , WO07115981 , WO08035571 , WO2002015645 , WO2003040257 , WO2005019373 , WO2006056418 , WO2008054584 , WO2008078800 , WO2008096609 , WO2008101842 , WO2009000673 , WO2009050281 , WO2009100991 , WO2010028151 , WO2010054731 , WO2010086089 , WO2010118029 , WO2011044988 , WO2011051404 , WO2011107491 , WO2012020327 , WO2012163471 , WO2013094620 , WO2013107487 , WO2013174471 , WO2014007565 , WO2014008982 , WO2014023377 , WO2014024131 , WO2014031977 , WO2014038456 , WO2014112450 .

f) HBL:

A hole blocking layer (HBL) may be used to reduce the number of holes and/or excitons that leave the emissive layer. The presence of such a blocking layer in a device may result in substantially higher efficiencies and/or longer lifetime as compared to a similar device lacking a blocking layer. Also, a blocking layer may be used to confine emission to a desired region of an OLED. In some embodiments, the HBL material has a lower HOMO (further from the vacuum level) and/or higher triplet energy than the emitter closest to the HBL interface. In some embodiments, the HBL material has a lower HOMO (further from the vacuum level) and/or higher triplet energy than one or more of the hosts closest to the HBL interface.
In one aspect, compound used in HBL contains the same molecule or the same functional groups used as host described above.
In another aspect, compound used in HBL contains at least one of the following groups in the molecule:
wherein k is an integer from 1 to 20; L¹⁰¹ is another ligand, k' is an integer from 1 to 3.

g) ETL:

Electron transport layer (ETL) may include a material capable of transporting electrons. Electron transport layer may be intrinsic (undoped), or doped. Doping may be used to enhance conductivity. Examples of the ETL material are not particularly limited, and any metal complexes or organic compounds may be used as long as they are typically used to transport electrons.
In one aspect, compound used in ETL contains at least one of the following groups in the molecule:

wherein R¹⁰¹ is selected from the group consisting of hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acids, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof, when it is aryl or heteroaryl, it has the similar definition as Ar's mentioned above. Ar¹ to Ar³ has the similar definition as Ar's mentioned above. k is an integer from 1 to 20. X¹⁰¹ to X¹⁰⁸ is selected from C (including CH) or N.
In another aspect, the metal complexes used in ETL contains, but not limit to the following general formula:
wherein (O-N) or (N-N) is a bidentate ligand, having metal coordinated to atoms O, N or N, N; L¹⁰¹ is another ligand; k' is an integer value from 1 to the maximum number of ligands that may be attached to the metal.
Non-limiting examples of the ETL materials that may be used in an OLED in combination with materials disclosed herein are exemplified below together with references that disclose those materials: CN103508940 , EP01602648 , EP01734038 , EP01956007 , JP2004-022334 , JP2005149918 , JP2005-268199 , KR0117693 , KR20130108183 , US20040036077 , US20070104977 , US2007018155 , US20090101870 , US20090115316 , US20090140637 , US20090179554 , US2009218940 , US2010108990 , US2011156017 , US2011210320 , US2012193612 , US2012214993 , US2014014925 , US2014014927 , US20140284580 , US6656612 , US8415031 , WO2003060956 , WO2007111263 , WO2009148269 , WO2010067894 , WO2010072300 , WO2011074770 , WO2011105373 , WO2013079217 , WO2013145667 , WO2013180376 , WO2014104499 , WO2014104535 ,

h) Charge generation layer (CGL)

In tandem or stacked OLEDs, the CGL plays an essential role in the performance, which is composed of an n-doped layer and a p-doped layer for injection of electrons and holes, respectively. Electrons and holes are supplied from the CGL and electrodes. The consumed electrons and holes in the CGL are refilled by the electrons and holes injected from the cathode and anode, respectively; then, the bipolar currents reach a steady state gradually. Typical CGL materials include n and p conductivity dopants used in the transport layers.
In any above-mentioned compounds used in each layer of the OLED device, the hydrogen atoms can be partially or fully deuterated. The minimum amount of hydrogen of the compound being deuterated is selected from the group consisting of 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95%, 99%, and 100%. Thus, any specifically listed substituent, such as, without limitation, methyl, phenyl, pyridyl, etc. may be undeuterated, partially deuterated, and fully deuterated versions thereof. Similarly, classes of substituents such as, without limitation, alkyl, aryl, cycloalkyl, heteroaryl, etc. also may be undeuterated, partially deuterated, and fully deuterated versions thereof.
It is understood that the various embodiments described herein are by way of example only and are not intended to limit the scope of the invention. For example, many of the materials and structures described herein may be substituted with other materials and structures without deviating from the spirit of the invention. The present invention as claimed may therefore include variations from the particular examples and preferred embodiments described herein, as will be apparent to one of skill in the art. It is understood that various theories as to why the invention works are not intended to be limiting.

E. Experimental Data

Synthesis Examples

Synthesis Example 1

Di-µ-chloro-tetrakis[k2(C2,N)-5-(methyl-d₃ )-2-((6-(methyl-d₃ )-[1,1'-biphenyl]-3-yl)-4'-yl)pyridin-1-yl]diiridiium(III)

A mixture of 5-(methyl-d ₃)-2-(6-(methyl-d ₃)-[1,1'-biphenyl]-3-yl)pyridine (35.2 g, 133 mmol, 2.1 equiv) and iridium(III) chloride hydrate (20 g, 63.2 mmol, 1.0 equiv) in diglyme (550 mL) and water (82 mL) was sparged with nitrogen for 30 minutes then heated at reflux over the weekend for 48 hours. The cooled reaction mixture was filtered, the solid washed with methanol (2 × 150 mL) and dried in a vacuum oven at 60 °C for 16 hours to afford di-µ-chloro-tetrakis[k2(C2,N)-5-(methyl-d₃ )-2-((6-(methyl-d₃ )-[1,1'-bi-phenyl]-3-yl)-4'-yl)pyridin-1-yl]diiridiium(III) (43 g, 90% yield) as a yellow solid.

[Ir((5-(methyl-d₃ )-2-((6-(methyl-d₃ )-[1,1'-biphenyl]-3-yl)-4'-yl)pyridin-1-yl](-1H))₂(MeOH)₂] trifluoromethanesulfonate

A solution of silver trifluoromethanesulfonate (15.92 g, 61.9 mmol, 2.2 equiv) in methanol (147 mL) was added to a solution of di-µ-chloro-tetrakis[k2(C2,N)-5-(methyl-d₃ )-2-((6-(methyl-d₃ )-[1,1'-bi-phenyl]-3-yl)-4'-yl)pyridin-1-yl]diiridiium(III) (42.6 g, 28.2 mmol, 1.0 equiv) in dichloromethane (733 mL) in a flask wrapped with aluminum foil to exclude light. The reaction mixture was stirred at room temperature (RT) overnight. Stirring was stopped and the solids allowed to settle for 1 hour to aid filtration. The reaction mixture was filtered through a short (~2 inch) silica gel pad, rinsing the flask and pad with dichloromethane (1.0 L) until no yellow color remained on the pad. The filtrate was concentrated under reduced pressure and the solid dried under vacuum at 40 °C for 4 hours to give [Ir((5-(methyl-d₃ )-2-((6-(methyl-d₃ )-[1,1'-biphenyl]-3-yl)-4'-yl)pyridin-1-yl](-1H))₂-(MeOH)₂] trifluoromethanesulfonate)(49.6 g, 94% yield) as a yellow solid.

Mer-Bis[5-(methyl-d ₃)-2-(6-(methyl-d ₃)-[1,1'-biphenyl]-3-yl)-4'-yl)pyridin-1-yl]-[4-(4-(2,2-dimethylpropyl-1,1-d ₂)phenyl)-(2-phenyl-2'-yl)pyridin-1-yl]-iridium(III)

A solution of [Ir((5-(methyl-d₃ )-2-((6-(methyl-d₃ )-[1,1'-biphenyl]-3-yl)-4'-yl)pyridin-1-yl](-1H))₂(MeOH)₂] trifluoromethane-sulfonate (8 g, 8.56 mmol, 1.0 equiv), 4-(4-(2,2-dimethylpropyl-1,1-d ₂)phenyl)-2-phenylpyridine (2.86 g, 9.42 mmol, 1.1 equiv) and triethylamine (5.97 mL, 42.8 mmol, 5.0 equiv) in acetone (245 mL) was heated at 50 °C for 48 hours. Liquid chromatography-mass spectrometry (LC-MS) analysis showed compound mer (69%). The cooled reaction mixture was concentrated under reduced pressure. A solution of the residue in dichloromethane (20 mL) was filtered to remove dark insoluble material. The filtrate was passed through a pad of Celite (100 g), rinsing with dichloromethane (100 mL) and the filtrate concentrated under reduced pressure. The solid was dissolved in 20% methanol in dichloromethane (100 mL) then precipitated by addition of methanol (100 mL). The suspension was stirred for 15 minutes, the fine yellow solid filtered and washed with methanol (200 mL). The solid was dried in a vacuum oven at 50 °C for overnight to give compound mer-complex (8.1 g, 85% LCMS purity, 90% Q-NMR purity), as a yellow solid.

Bis[5-(methyl-d ₃)-2-(6-(methyl-d ₃)-[1,1'-biphenyl]-3-yl)-2'-yl)pyridin-1-yl][4-(4-(2,2-dimethylpropyl-1,1-d ₂)phenyl)-(2-phenyl-2'-yl)pyridin-1-yl]iridium(III)

The meridonal isomer was converted to the facial isomer via photoisomerization

Purification

Crude compound after photoreaction (8.0 g, 87.8% purity), containing residual mer-isomer, (1.8%) was filtered through a pad of basic alumina (100 g), eluting with dichloromethane (1 L). The filtrate was concentrated under reduced pressure. The residue was purified on a Biotage automated chromatography system (2 stacked 100 g Biotage silica gel cartridges), eluting with 12-100% tetrahydrofuran in heptanes, to give a sticky yellow solid. The solid (5 g) was dissolved in dichloromethane (5 mL) then precipitated by addition of methanol (100 mL). The solid was filtered, washed with methanol (50 mL) and dried in a vacuum oven at 50 °C overnight to give fac compound (4.1 g, 99.8% UPLC purity) as a yellow solid. The solid was precipitated from dichloromethane in hexanes (5 mL/100 mL) then dried in a vacuum oven at 50 °C overnight to give bis[5-(methyl-d ₃)-2-(6-(methyl-d ₃)-[1,1'-biphenyl]-3-yl)-2'-yl)pyridin-1-yl] [4-(4-(2,2-dimethylpropyl-1,1-d ₂)phenyl)-(2-phenyl-2'-yl)pyridine-1-yl]iridium(III) (3.9 g, 45% yield, 99.8% UPLC purity), as a yellow solid.

Synthesis Example 2

Di-µ-chloro-tetrakis[k2(C2,N)-1-(2,6-bis(propan-2-yl-d₇ )phenyl)-(2-(6-(methyl-d₃ )-[1,1'-biphenyl]-3-yl)-2'-yl)-1H-benzo [d]imidazol-3-yl]diiridium(III)

A mixture of 1-(2,6-bis(propan-2-yl-d₇ )phenyl)-2-(6-(methyl-d₃ )-[1,1'-bi-phenyl]-3-yl)-1H-benzo[d]imidazole (5.3 g, 11.54 mmol, 2.2 equiv) and iridium(III) chloride hydrate (1.66 g, 5.24 mmol, 1.0 equiv) in 2-ethoxyethanol (80 mL) and water (26 mL) was heated at 102 °C for 70 hours. The cooled reaction mixture was filtered, the solid washed with methanol (3 × 50 mL) then dried in a vacuum oven at ~50 °C for a few hours to give di-µ-chloro-tetrakis-[k2(C2,N)-1-(2,6-bis(propan-2-yl-d₇ )phenyl)-(2-(6-(methyl-d₃ )-[1,1'-biphenyl]-3-yl)-2'-yl)-1H-benzo[d]imidazol-3-yl]diiridium(III) (4.76 g, 79% yield) as a yellow solid.

[Ir(1-(2,6-bis(propan-2-yl-d₇ )phenyl)-(2-(6-(methyl-d₃ )-[1,1'-biphenyl]-3-yl)-2'-yl)-1H-benzo[d]imidazol-3-yl)(1H)₂(MeOH)₂] trifluoromethanesulfonate

A solution of silver trifluoromethanesulfonate (1.16 g, 4.55 mmol, 2.2 equiv) in methanol (15 mL) was added in one portion to a solution of di-µ-chloro-tetrakis[k2(C2,N)-1-(2,6-bis(propan-2-yl-d₇ )ρhenyl)-(2-(6-(methyl-d₃ )-[1,1'-biphenyl]-3-yl)-2'-yl)-1H-benzo[d]imidazol-3-yl]diiridium(III) (4.75 g, 2.06 mmol, 1.0 equiv) in dichloromethane (75 mL) and the flask wrapped with aluminum foil to exclude light. The reaction mixture was stirred at RT overnight under nitrogen. The reaction mixture was filtered through a ~1 inch pad of silica gel, rinsing with dichloromethane (2 × 100 mL) then a 5:1 mixture of dichloromethane and methanol (2 × 100 mL). The filtrate was concen-trated under reduced pressure and the residue dried in a vacuum oven at 50 °C overnight to give [Ir(1-(2,6-bis(propan-2-yl-d₇ )phenyl)-(2-(6-(methyl-d₃ )-[1,1'-bi-phenyl]-3-yl)-2'-yl)-1H-benzo[d]imidazol-3-yl)(1H)₂(MeOH)₂] trifluoromethane-sulfonate (5.3 g, 97% yield) as a yellow-greenish solid.

Bis[1-(2,6-bis(propan-2-yl-d₇ )phenyl)-(2-(6-(methyl-d₃ )-[1,1'-biphenyl]-3-yl)-4'-yl)-1H-benzo[d]imidazol-3-yl]-[(2-(dibenzo[b,d]furan-4-yl)-3'-yl)-4-(4-(2,2-dimethylpropyl-1,1-d₂ )phenyl)pyridin-1-yl)iridium(III)

A mixture of [Ir(1-(2,6-bis(propan-2-yl-d₇ )phenyl)-(2-(6-(methyl-d₃ )-[1,1'-biphenyl]-3-yl)-2'-yl)-1H-benzo[d]imidazol-3-yl)(1H)₂(MeOH)₂] trifluoromethane-sulfonate (5.0 g, 3.77 mmol, 1.0 equiv) and 2-(dibenzo[b,d]furan-4-yl)-4-(4-(2,2-dimethylpropyl-1,1-d₂ )phenyl)pyridine (1.49 g, 3.77 mmol, 1.0 equiv) in ethanol (70 mL) was heated at 78 °C for 2 hours then 2,6-lutidine (0.404 g, 3.77 mmol, 1.0 equiv) added. The reaction mixture was heated at 78 °C for 27 hours, cooled to room temperature then concentrated under reduced pressure. The residue was dissolved in dichloromethane (~40 mL) and the solution loaded onto a Biotage automated chromatography system (2 stacked 220 g and one 330 g silica gel cartridges), eluting with a gradient of 0-25% toluene in hexanes. The recovered product (3.3 g) was filtered through basic alumina (450 g), eluting with 50% dichloromethane in hexanes. The obtained solid (3.2 g) was dissolved in dichloromethane (40 mL) then precipitated with methanol (260 mL) to give bis[1-(2,6-bis(propan-2-yl-d₇ )phenyl)-(2-(6-(methyl-d₃ )-[1,1'-biphenyl]-3-yl)-4'-yl)-1H-benzo[d]imidazol-3-yl]-[(2-(dibenzo-[b,d]furan-4-yl)-3'-yl)-4-(4-(2,2-dimethylpropyl-1,1-d₂ )phenyl-2,6-d₂ )pyridin-1-yl)-iridium(III) (3.1 g, 54% yield, 99.7% UPLC purity) as a red-orange solid.

Synthesis Example 3

[Ir(4,5-bis(methyl-d₃ )-2-(6-(methyl-d₃ )[1,1'-biphenyl]-4'-yl)pyridin-1-yl)(-1H))₂-[MeOH)₂] trifluoromethanesulfonate

A solution of silver trifluoromethanesulfonate (195 g, 758 mmol, 2.2 equiv) in methanol (1800 mL) was added to a solution of di-µ-chloro-tetrakis[k2(C2,N)-4,5-bis(methyl-d₃ )-2-(6-(methyl-d₃ )-[1,1'-biphenyI]-4'-yl)pyridin-1-yl]diiridiium(III) (545 g, 345 mmol, 1.0 equiv) in dichloromethane (9000 mL) in a flask wrapped with aluminum foil to exclude light. The reaction mixture was stirred at RT overnight then filtered through silica gel (~1 kg), washing with dichloromethane (4 L). The filtrate was concentrated under reduced pressure and the residue dried in a vacuum oven at 50 °C over two days to give [Ir(4,5-bis-(methyl-d₃ )-2-(6-(methyl-d₃ )-[1,1'-biphenyl]-4'-yl)pyridin-1-yl)(1H))₂(MeOH)₂] trifluoromethanesulfonate (661 g, 99% yield) as a yellow solid.

mer-Bis[4,5-bis(methyl-d₃ )-2-(6-(methyl-d₃ )-[1,1'-biphenyl]-4'-yl)pyridin-1-yl]-[4-(4-(2,2-dimethylpropyl-1,1-d₂ )phenyl)-2-((naphtho[1,2-b]benzo-furan-10-yl)-9'-yl)pyridin-1-yl]iridium(III)

A 250 mL, 4-neck flask was charged with [Ir(4,5-bis(methyl-d₃ )-2-(6-(methyl-d₃ )-[1,1'-bi-phenyl]-4'-yl)pyridin-1-yl)(1H))₂(MeOH)₂] trifluoromethanesulfonate (4.25 g, 4.39 mmol, 1.0 equiv), 4-(4-(2,2-dimethylpropyl-1,1-d ₂)phenyl)-2-(naphtho[1,2-b]benzofuran-10-yl)pyridine (2.15 g, 4.83 mmol, 1.1 equiv) and acetone (137 mL). After stirring for several minutes, triethylamine (1.83 mL, 13.2 mmol, 3.0 equiv) was added then the reaction mixture heated at 50 °C for 22 hours. The reaction mixture was cooled to room temperature. Dichloromethane was added to dissolve most solids and the mixture filtered through Celite^® (diatomaceous earth)(5 g). The filtrate was concentrated under reduced pressure to give an orange solid which was triturated with 20% dichloromethane in methanol (100 mL) at 35 °C for one hour. The cooled suspension was filtered and the solid dried in a vacuum oven overnight at 50 °C to give mer-complex (5.44 g, >100% yield) as an orange solid.

Bis[4,5-bis(methyl-d₃ )-2-(6-(methyl-d₃ )-[1,1'-biphenyl]-4'-yl)pyridin-1-yl][4-(4-(2,2-dimethylpropyl-1,1-d ₂)phenyl-2,6-d ₂)-2-((naphtho[1,2-b]benzofuran-10-yl)-9'-yl)pyridin-1-yl]Iridium(III) (2021-ADS-UDC-Ir984)

The meridonal isomer was converted to the facial isomer via photoisomerization.
Solvent wet crude after photoreaction (4.74 g) was filtered through basic alumina (100 g) atop silica gel (20 g), eluting with dichloromethane (1.0 L). Product fractions were concentrated under reduced pressure. The residue was purified on a Biotage automated chromatography system (2 stacked, 350 g HC cartridges), eluting with 0-30% tetrahydrofuran in hexanes. Clean product fractions were saved. Mixed fractions were combined into two batches based on impurity profiles and re-purified using similar conditions. All pure fractions were concentrated under reduced pressure. The orange solid was dissolved in dichloromethane (50 mL), precipitated with methanol (50 mL), filtered and dried in a vacuum oven overnight at 50 °C to give bis[4,5-bis(methyl-d₃ )-2-(6-(methyl-d₃)-[1,1'-biphenyl]-4'-yl)pyridin-1-yl][4-(4-(2,2-dimethylpropyl-1,1-d ₂)phenyl)-2-((naphtho[1,2-b]benzofuran-10-yl)-9'-yl)pyridin-1-yl]Iridium(III) (2.69 g, 51% yield, 99.9% UPLC purity) as an orange solid.

Synthesis Example 4

Di-µ-chloro-tetrakis[k2(C2,N)-1-(2,6-bis(propan-2-yl-d₇ )phenyl)-(2-(6-(methyl-d₃ )-[1,1'-biphenyl]-3-yl)-2'-yl)-1H-benzo[d]imidazol-3-yl]diiridium(III)

[Ir(1-(2,6-bis(propan-2-yl-d₇ )phenyl)-(2-( 6-(methyl-d₃ )-[1,1'-biphenyl]-3-yl)-2'-yl)-1H-benzo[d]imidazol-3-yl)(1H)₂(MeOH)₂] trifluoromethanesulfonate

A solution of silver trifluoromethanesulfonate (1.16 g, 4.55 mmol, 2.2 equiv) in methanol (15 mL) was added in one portion to a solution of di-µ-chloro-tetrakis[k2(C2,N)-1-(2,6-bis(propan-2-yl-d₇ )ρhenyl)-(2-(6-(methyl-d₃ )-[1,1'-biphenyl]-3-yl)-2'-yl)-1H-benzo[d]imidazol-3-yl]diiridium(III) (4.75 g, 2.06 mmol, 1.0 equiv) in dichloromethane (75 mL) and the flask wrapped with aluminum foil to exclude light. The reaction mixture was stirred at RT overnight under nitrogen. The reaction mixture was filtered through a ~1 inch pad of silica gel, rinsing with dichloromethane (2 × 100 mL) then dichloromethane in methanol (5:1, 2 × 100 mL). The filtrate was concentrated under reduced pressure and the residue dried in a vacuum oven at 50 °C overnight to give [Ir(1-(2,6-bis(propan-2-yl-d₇ )phenyl)-(2-(6-(methyl-d₃ )-[1'-biphenyl]-3-yl)-2'-yl)-1H-benzo[d]imidazol-3-yl)(1H)₂(MeOH)₂] trifluoromethane-sulfonate (5.3 g, 97% yield) as a yellow-greenish solid.

Bis[1-(2,6-bis(propan-2-yl-d ₇)phenyl)-2-((6-(methyl-d ₃)-[1,1'-biphenyl]-3-yl)-4'-yl)-1H-benzo[d]imidazol-1-yl][4-(4-(2,2-dimethylpropyl-1,1-d ₂)phenyl)-2-((naphtho[1,2-b]benzofuran-10-yl)-4'-yl)pyridin-1-yl]Iridium(III)

A 500 mL 4-neck flask was charged with [Ir(1-(2,6-bis(propan-2-yl-d₇ )phenyl)-(2-(6-(methyl-d₃ )-[1,1'-biphenyl]-3-yl)-2'-yl)-1H-benzo[d]imidazol-3-yl)(1H)₂(MeOH)₂] trifluoromethanesulfonate (4.40 g, 3.35 mmol, 1.0 equiv), 4-(4-(2,2-dimethylpropyl-1,1-d ₂)phenyl-2,6-d ₂)-2-(naphtho[1,2-b]benzofuran-10-yl)pyridine (lot# KRM2021-2-088, 1.49 g, 3.35 mmol, 1.0 equiv) and ethanol (167 mL). 2,6-Lutidine (0.388 mL, 3.35 mmol, 1.0 equiv) was added then the reaction mixture heated at 75 °C for 15.5 hours. LCMS analysis indicated 75% conversion. The reaction mixture was cooled to RT, the suspension filtered and the solid rinsed with methanol (20 mL). The crude orange solid (3.95 g) was purified on a Biotage automated chromatography system (2 stacked 350 g silica gel cartridges), eluting with 0-30% tetrahydrofuran in hexanes, to give two batches of mixed fractions. Each batch was re-purified separately on a Biotage automated chromatography system (4 stacked 100 g silica gel cartridges), eluting with 0-20% tetrahydrofuran in hexanes. Purest product fractions were concentrated under reduced pressure. The residue was dissolved in dichloromethane (100 mL) and precipitated with methanol (50 mL) to give an orange solid (99.0% UPLC purity). The material was divided into two equal parts and each re-chromato-graphed on a Biotage system (4 stacked 100 g silica gel cartridges), eluting with 10-30% toluene in hexanes containing 5% dichloromethane. Pure fractions were concentrated under reduced pressure. The residue was precipitated from dichloromethane (120 mL) with methanol (100 mL) then filtered. The solid was dried in a vacuum oven overnight at 50 °C to give bis[1-(2,6-bis(propan-2-yl-d ₇)--phenyl)-2-((6-(methyl-d ₃)-[1,1'-biphenyl]-3-yl)-4'-yl)-1H-benzo[d]imidazol-1-yl]-[4-(4-(2,2-dimethylpropyl-1,1-d ₂)phenyl)-2-((naphtho[1,2-b]benzofuran-10-yl)-4'-yl)pyridin-1-yl]Iridium(III) (2.29 g, 43% yield, 99.6% UPLC purity) as an orange solid.

Synthesis Example 5

A solution of silver trifluoromethanesulfonate (1.16 g, 4.55 mmol, 2.2 equiv) in methanol (15 mL) was added in one portion to a solution of di-µ-chloro-tetrakis[k2(C2,N)-1-(2,6-bis(propan-2-yl-d₇ )ρhenyl)-(2-(6-(methyl-d₃ )-[1,1'-biphenyl]-3-yl)-2'-yl)-1H-benzo[d]imidazol-3-yl]diiridium(III) (4.75 g, 2.06 mmol, 1.0 equiv) in dichloromethane (75 mL) and the flask wrapped with aluminum foil to exclude light. The reaction mixture was stirred at room temperature overnight under nitrogen. The reaction mixture was filtered through a ~1 inch pad of silica gel, rinsing with dichloromethane (2 × 100 mL) then dichloromethane in methanol (5:1, 2 × 100 mL). The filtrate was concentrated under reduced pressure and the residue dried in a vacuum oven at 50 °C overnight to give [Ir(1-(2,6-bis(propan-2-yl-d₇ )phenyl)-(2-(6-(methyl-d₃ )-[1,1'-biphenyl]-3-yl)-2'-yl)-1H-benzo[d]imidazol-3-yl)(1H)₂(MeOH)₂] trifluoromethane-sulfonate (5.3 g, 97% yield) as a yellow-greenish solid.

Bis[1-(2,6-bis(propan-2-yl-d₇ )phenyl)-(2-(6-(methyl-d₃ )-[1,1'-biphenyl]-3-yl)-4'-yl)-1H-benzo[d]imidazol-3-yl]-[4-(4-(2,2-dimethylpropyl-1,1-d₂ )phenyl)-2-(phenyl-2'-yl)pyridin-1-yl]iridium(III)

A mixture of [Ir(1-(2,6-bis(propan-2-yl-d₇ )phenyl)-(2-(6-(methyl-d₃ )-[1,1'-biphenyl]-3-yl)-2'-yl)-1H-benzo[d]imidazole-3-yl)(1H)₂(MeOH)₂] trifluoromethanesulfonate (3.94 g, 2.97 mmol, 1.0 equiv), 4-(4-(2,2-dimethylpropyl-1,1-d₂ )phenyl)-2-phenylpyridine (0.9 g, 2.97 mmol, 1.0 equiv) and 2,6-lutidine (0.318 g, 2.97 mmol, 1.0 equiv) in ethanol (55 mL) was heated at 78 °C for 19 hours. The cooled reaction mixture was concentrated under reduced pressure to give ~4 g of crude material. The material was purified in 2 portions on a Büchi automated chromatography system (7 stacked 120 g silica gel cartridges), eluting with a gradient of 0-4% acetone in hexanes. The recovered product (1.8 g) was filtered through basic alumina (550 g), eluting with 50-100% dichloromethane in hexanes. The obtained solid (1.7 g) was dissolved in dichloromethane (4 mL) and precipitated with methanol (200 mL). The solid was filtered and dried in a vacuum oven at ~50 °C overnight to give bis[1-(2,6-bis-(propan-2-yl-d₇ )phenyl)-(2-(6-(methyl-d₃ )-[1,1'-biphenyl]-3-yl)-4'-yl)-1H-benzo[d]-imidazol-3-yl]-[4-(4-(2,2-dimethylpropyl-1,1-d₂ )phenyl)-2-(phenyl-2'-yl)pyridin-1-yl]iridium(III) (1.67 g, 40% yield, 99.9% UPLC purity) as a red orange solid.

Synthesis Example 6

A mixture of 5-(methyl-d₃ )-2-(6-(methyl-d₃ )-[1,1'-biphenyl]-3-yl)pyridine (30.6 g, 115 mmol, 2.1 equiv) and iridium(III) chloride hydrate (17.4 g, 55 mmol, 1.0 equiv) in diglyme (500 mL) and water (75 mL) was sparged with nitrogen for 15 minutes then heated at reflux for 48 hours. The cooled reaction mixture was filtered, the solid washed with methanol (2 × 100 mL) and dried in a vacuum oven at 50 °C for 16 hours to afford di-µ-chloro-tetrakis[k2(C2,N)-5-(metlryl-d₃ )-2-((6-(methyl-d₃ )-[1,1'-bi-phenyl]-3 -yl)-4'-yl)pyridin-1-yl]diiridiium(III) (31.2 g, 75% yield) as a yellow solid.

[Ir((5-(methyl-d₃ )-2-((6-(methyl-d₃ )-[1,1'-biphenyl]-3-yl)-4'-yl)pyridin-1-yl](-1H))₂(MeOH)₂] trifluoromethanesulfonate

A solution of silver trifluoromethanesulfonate (12.4 g, 48.3 mmol, 2.2 equiv) in methanol (80 mL) was added to a solution of di-µ-chloro-tetrakis[k2(C2,N)-5-(methyl-d₃ )-2-((6-(methyl-d₃ )-[1,1'-bi-phenyl]-3-yl)-4'-yl)pyridin-1-yl]diiridiium(III) (33.0 g, 21.8 mmol, 1.0 equiv) in methylene chloride (525 mL) in a flask wrapped with aluminum foil to exclude light. The reaction mixture was stirred at RT for 16 hours then filtered through a ~1 inch pad of silica gel pad topped a ∼0.5 inch with Celite, rinsing with methylene chloride (1.0 L). The filtrate was concentrated under reduced pressure and the residue was re-dissolved in methylene chloride (150 mL) and methanol (50 mL). The solution was added dropwise to hexanes (1.0 L) and the flask rinsed with a small volume of methylene chloride. The precipitate was filtered and the precipitation method repeated. The solid obtained was dried under vacuum at 50 °C for 16 hours to give [Ir((5-(methyl-d₃ )-2-((6-(methyl-d₃ )-[1,1'-biphenyl]-3-yl)-4'-yl)pyridin-1-yl](-1H))₂(MeOH)₂] trifluoromethanesulfonate (28.8 g, 71% yield) as a yellow solid.

mer-Bis[(5-(methyl-d₃ )-2-(6-(methyl-d₃ )-[1,1'-biphenyl]-3-yl)-pyridin-1-yl)]-[2-((dibenzo[b,d]furan-4-yl)-3'-yl)-4-(4-(2,2-dimethylpropyl-1,1-d₂ )phenyl)pyridin-1-yl]iridium(III)

A nitrogen flushed 250 mL 4-neck flask was charged with [Ir((5-(methyl-d₃ )-2-((6-(methyl-d₃ )-[1,1'-biphenyl]-3-yl)-4'-yl)pyridin-1-yl](-1H))₂(MeOH)₂] trifluoromethanesulfonate (5.5 g, 5.89 mmol, 1.0 equiv), 2-(dibenzo[b,d]furan-4-yl)-4-(4-(2,2-di-methylpropyl-1,1-d₂ )phenyl)pyridine (2.56 g, 6.48 mmol, 1.1 equiv) and acetone (120 mL). The reaction mixture was sparged with nitrogen for 15 minutes and the flask wrapped in foil to exclude light. Triethylamine (2.46 mL, 17.66 mmol, 3.0 equiv) was added then the reaction mixture heated at 50 °C for 17 hours. The reaction mixture was cooled to RT then filtered through a pad of Celite^® (15 g), rinsing with dichloromethane (50 mL). The filtrate was concentrated under reduced pressure. The residue was triturated with 10% dichloromethane in methanol (30 mL). The solid was filtered and washed with methanol (20 mL) to give (7.4 g, 72% Q NMR purity) as a bright orange solid.

Bis[(5-(methyl-d₃ )-2-(6-(methyl-d₃ )-[1,1'-biphenyl]-3-yl)-pyridin-1-yl)][2-((dibenzo[b,d]furan-4-yl)-3'-yl)-4-(4-(2,2-dimethylpropyl-1,1-d₂)phenyl)pyridin-1-yl]iridium(III)

The meridonal isomer was converted to the facial isomer via photoisomerization.
Crude product after photoreaction (~ 8 g) was dissolved in dichloromethane (50 mL) and passed through a pad of silica gel (40 g) topped with basic alumina (190 g), eluting with 50% dichloromethane in hexanes (1 L). Product fractions were concentrated under reduced pressure. The residue was dissolved in dichloro-methane (65 mL), adsorbed onto Celite^® (16 g) and purified on a Biotage Isolera automated chromatography system (3 stacked 100 g Biotage silica gel cartridges), eluting with 0-20% tetrahydrofuran in hexanes. Pure product fractions were concentrated under reduced pressure. The residue was dissolved in dichloromethane (20 mL) and precipitated with methanol (30 mL). The solid was were filtered, washed with methanol (30 mL) and dried in a vacuum oven at 50 °C overnight to give bis[(5-(methyl-d₃ )-2-(6-(methyl-d₃ )-[1,1'-biphenyl]-3-yl)-pyridin-1-yl)][2-((dibenzo[b,d]furan-4-yl)-3'-yl)-4-(4-(2,2-dimethylpropyl-1,1-d₂ )-phenyl-2,6-d₂ )pyridin-1-yl]iridium(III) (3.9 g, 49% yield, 99.8% UPLC purity) as a bright yellow solid.

Synthesis Example 7

[Ir(4,5-bis(methyl-d₃ )-2-(6-(methyl-d₃ )[1,1'-biphenyl]-4'-yl)pyridin-1-yl)(-1H))₂(MeOH)₂] trifluoromethanesulfonate

A solution of silver trifluoromethanesulfonate (195 g, 758 mmol, 2.2 equiv) in methanol (1800 mL) was added to a solution of di-µ-chloro-tetrakis[k2(C2,N)-4,5-bis(methyl-d₃ )-2-(6-(methyl-d₃ )-[1,1'-biphenyl]-4'-yl)pyridin-1-yl]diiridiium(III) (545 g, 345 mmol, 1.0 equiv) in dichloromethane (9000 mL) in a flask wrapped with aluminum foil to exclude light. The reaction mixture was stirred at RT overnight then filtered through a pad of silica gel (~1 kg), washing with dichloromethane (4 L). The filtrate was concentrated under reduced pressure and the residue dried in a vacuum oven at 50 °C over two days to give [Ir(4,5-bis-(methyl-d₃ )-2-(6-(methyl-d₃)-[1,1'-biphenyl]-4'-yl)pyridin-1-yl)(1H))₂(MeOH)₂] trifluoromethane-sulfonate) (661 g, 99% yield) as a yellow solid.

Mer-Bis[(4,5-bis(methyl-d₃ )-2-(6-(methyl-d₃ )-[1,1'-biphenyl]-3-yl)pyridin-1-yl)]-[2-((dibenzo[b,d]furan-4-yl)-3'-yl)-4-(4-(2,2-dimethylpropyl-1,1-d₂ )phenyl-)pyridin-1-yl]iridium(III)

A nitrogen flushed 250 mL 4-neck flask was charged with [Ir(4,5-bis(methyl-d₃ )-2-(6-(methyl-d₃ )-[1,1'-biphenyl]-3-yl)pyridine(-H))₂(MeOH)₂] trifluoromethanesulfonate (6.0 g, 6.20 mmol, 1.0 equiv), 2-(dibenzo[b,d]furan-4-yl)-4-(4-(2,2-di-methylpropyl-1,1-d₂ )phenyl)pyridine (2.70 g, 6.82 mmol, 1.1 equiv) and acetone (125 mL). The mixture was sparged with nitrogen for 15 minutes and the flask wrapped in foil to exclude light. Triethylamine (2.59 mL, 18.6 mmol, 3.0 equiv) was added then the reaction mixture heated at 50 °C overnight. After 20 hours, the reaction mixture was cooled to RT and filtered through a pad of Celite^® (10 g), rinsing with dichloromethane (20 mL). The filtrate was concentrated under reduced pressure and the residue triturated with 10% dichloromethane in methanol (50 mL). The solid was filtered and washed with methanol (50 mL) to give solvent wet mer-complex (9.5 g, 74.4% QNMR purity) as an orange solid.

Bis[(4,5-bis(methyl-d₃ )-2-(6-(methyl-d₃ )-[1,1'-biphenyl]-3-yl)pyridin-1-yl)]-[2-((dibenzo[b,d]furan-4-yl)-3'-yl)-4-(4-(2,2-dimethylpropyl-1,1-d₂ )phenyl-2,6-d₂ )pyridin-1-yl]iridium(III))

The meridonal isomer was converted to the facial isomer via photoisomerization.

Purification:

Crude product after photo isomerization (8 g) was partially purified by chromatography on silica gel (~40 g) topped with basic alumina (~250 g), eluting with 50% dichloromethane in hexanes (1 L). Product fractions were concentrated under reduced pressure. The residue was dissolved in dichloromethane (50 mL) and adsorbed onto Celite^® (14 g). The adsorbed material was purified on a Biotage Isolera automated chromatography system (3 stacked 100 g HC Biotage silica gel cartridges), eluting with 30-50% toluene in hexanes. Pure product fractions were concentrated under reduced pressure. The residue was dissolved in dichloromethane (15 mL) and precipitated with methanol (50 mL). The solid was, washed with methanol (30 mL) and dried under vacuum at 50 °C overnight to give bis[(4,5-bis(methyl-d₃ )-2-(6-(methyl-d₃ )-[1,1'-biphenyl] -3 -yl)pyridin-1-yl)] -[2-((dibenzo [b,d]furan-4-yl)-3'-yl)-4-(4-(2,2-dimethylpropyl-1,1-d₂ )phenyl-2,6-d₂ )-pyridin-1-yl]iridium(III) (3.8 g, 47.5% yield, >99.9% UPLC purity) as a bright yellow solid.

Synthesis Example 8

[Ir(4,5-bis(methyl-d₃ )-2-(4-(methyl-d₃ )phenyl)pyridine(-1H))₂(MeOH)₂](tri-fluoromethanesulfonate)

To a solution of di-µ-chloro-tetrakis [κ2(C2,N)-4,5-bis(methyl-d ₃)-2-(4-(methyl-d ₃)-phenyl)pyridine]diiridium(III) (106 g 122 mmol, 1.0 equiv) in dichloromethane (2.0 L) was added a solution of silver trifluoromethanesulfonate (69.3 g, 270 mmol, 2.2 equiv) in methanol (500 mL) added. The flask was wrapped with foil to exclude light then the reaction mixture was stirred overnight at RT under nitrogen. The reaction mixture was filtered through a pad of silica gel (300 g) topped with Celite^® (20 g), rinsing with dichloromethane (1.0 L). The filtrate was concentrated under reduced pressure and the residue dried in a vacuum oven to give [Ir(4,5-bis(methyl-d ₃)-2-(4-(methyl-d ₃)phenyl)pyridine(-1H))₂-(MeOH)₂] trifluoromethanesulfonate (~162.5 g, 81% yield) as a yellow solid.

mer-Bis[4,5-bis(methyl-d ₃)-2-(4-(methyl-d ₃)phen-2'-yl)pyridin-1-yl]-[4-(4-(2,2-dimethylpropyl-1,1-d ₂)phenyl)-2-((naphtho[1,2-b]benzofuran-10-yl)-9'-yl)pyridin-1-yl]Iridium(III)

A 250 mL, 4-neck flask was charged with [Ir(4,5-bis(methyl-d ₃)-2-(4-(methyl-d ₃)phenyl)pyridine(-1H))₂-(MeOH)₂] trifluoromethanesulfonate (4.00 g, 4.90 mmol, 1.0 equiv), 4-(4-(2,2-dimethylpropyl-1,1-d ₂)phenyl)-2-(naphtho[1,2-b]benzofuran-10-yl)pyridine (2.40 g, 5.39 mmol, 1.1 equiv) and acetone (153 mL) then the mixture was stirred for several minutes under a nitrogen atmosphere. Triethylamine (2.05 mL, 14.7 mmol, 3.0 equiv) was added then the reaction mixture heated at 50°C for 18 hours. The reaction mixture was removed from heat and allowed to cool to RT. The reaction mixture was filtered through a pad of Celite^® (5 g), rinsing with dichloromethane (1.0 L). The filtrate was concentrated to give a red-orange solid which was triturated with 20% dichloromethane in methanol (100 mL) at 35 °C for one hour. The suspension was cooled to RT, filtered and the solid rinsed with methanol (50 mL). The solid was dried in a vacuum oven overnight at 50 °C to give mer-complex (4.47 g) as an orange solid.

Bis[4,5-bis(methyl-d ₃)-2-(4-(methyl-d ₃)phen-2'-yl)pyridin-1-yl]-[4-(4-(2,2-di-methylpropyl-1,1-d ₂)phenyl)-2-((naphtho[1,2-b]benzofuran-10-yl)-9'-yl)pyridin-1-yl]Iridium(III)

The meridonal isomer was converted to the facial isomer via photoisomerization.

Purification:

Crude compound after photoreaction (~5.0 g, wet) was filtered through a 1 inch pad of basic alumina atop a 1 inch pad of silica gel (1 × 1 inch), eluting with dichloromethane (1.0 L). Product fractions were concentrated under reduced pressure to give a red-orange solid. The recovered material was purified on a Biotage automated chromatography system (2 stacked 350 g silica gel cartridges), eluting with 0-30% tetrahydrofuran in hexanes. Cleanest product fractions concentrated under reduced pressure. The solid was precipitated from dichloromethane (50 mL) with methanol (50 mL) to give, after drying in a vacuum oven overnight at 50°C, bis[4,5-bis(methyl-d ₃)-2-(4-(methyl-d ₃)phen-2'-yl)pyridin-1-yl] [4-(4-(2,2-dimethylpropyl-1,1-d ₂)phenyl)-2-((naphtho[1,2-b]benzo-furan-10-yl)-9'-yl)pyiidin-1-yl]Iridium(III) (2.63 g, 51%yield, 99.5% UPLC purity) as an orange solid.

Synthesis Example 9

Di-µ-chloro-tetrakis[k2(C2,N)-1-(2,6-bis(propan-2-yl-d₇ )phenyl)-2-(4-(methyl-d₃ )phenyl-2'-yl)-1H-benzo [d]imidazol-3-yl] diiridium(III)

A mixture of 1-(2,6-bis(propan-2-yl-d₇ )phenyl)-2-(4-(methyl-d₃ )phenyl)-1H-benzo[d]imidazole (7 g, 18.21 mmol, 2.2 equiv) and iridium(III) chloride hydrate (2.62 g, 8.28 mmol, 1.0 equiv) in 2-ethoxyethanol (90 mL) and DIUF water (30 mL) was heated at 102 °C for 70 hours. The cooled reaction mixture was filtered, the solid washed with methanol (3 × 50 mL) then dried in a vacuum oven for a few hours at ~50 °C to give di-µ-chloro-tetrakis[k2(C2,N)-1-(2,6-bis(propan-2-yl-d₇ )phenyl)-2-(4-(methyl-d₃ )phenyl-2'-yl)-1H-benzo[d]imid-azol-3-yl]diiridium (III) (7.08 g, 86% yield) as a yellow solid.

[Ir(1-(2,6-bis(propan-2-yl-d₇ )phenyl)-2-(4-(methyl-d₃ )phenyl-2'-yl)-1H-benzo[d]imidazol-3-yl)(1H)₂(MeOH)₂] trifluoromethanesulfonate

A solution of silver trifluoromethanesulfonate (1.85 g, 7.21 mmol, 2.2 equiv) in methanol (18 mL) was added in one portion to a solution of di-µ-chloro-tetra-kis(k2(C2,N)-1-(2,6-bis(propan-2-yl-d₇ )phenyl)-2-(4-(methyl-d₃ )phenyl-2'-yl)-1H-benzo[d]imidazol-3-yl]diiridium (III) (7 g, 3.26 mmol, 1.0 equiv) in dichloromethane (90 mL) and the flask wrapped with foil to exclude light. The reaction mixture was stirred at RT overnight under nitrogen. The reaction mixture was filtered through a short (~1 inch) pad of silica gel, rinsing with dichloromethane (2 × 100 mL) then a 5:1 mixture of dichloromethane and methanol (2 × 100 mL). The filtrate was concentrated under reduced pressure and the residue dried in a vacuum oven at 50 °C overnight to give [Ir(1-(2,6-bis-(propan-2-yl-d₇ )phenyl)-2-(4-(methyl-d₃ )phenyl-2'-yl)-1H-benzo[d]imidazol-3-yl)-(1H)₂(MeOH)₂] trifluoromethanesulfonate (7.9 g, 103% yield) as a yellow-greenish solid.

Bis[1-(2,6-bis(propan-2-yl-d₇ )phenyl)-2-(4-(methyl-d₃ )phenyl-2'-yl)-1H-benzo[d]imidazol-3-yl]-[(2-(dibenzo[b,d]furan-4-yl)-3'-yl)-4-(4-(2,2-dimethyl-propyl-1,1-d₂)phenyl)pyridin-1-yl)iridium(III)

A mixture of [Ir(1-(2,6-bis(propan-2-yl-d₇ )phenyl)-2-( 4-(methyl-d₃ )phenyl-2'-yl)-1H-benzo[d]imidazol-3-yl)(1H)₂(MeOH)₂] trifluoromethanesulfonate (2.6 g, 2.21 mmol, 1.0 equiv) and 2-(dibenzo[b,d]furan-4-yl)-4-(4-(2,2-dimethyl-propyl-1,1-d₂ )pheny_l)pyridine (0.876 g, 2.21 mmol, 1.0 equiv) in ethanol (40 mL) was heated at 78 °C for 2 hours then 2,6-lutidine (0.237 g, 2.21 mmol, 1.0 equiv) added. The reaction mixture was heated at 78 °C for 30 hours, cooled to room temperature then concentrated under reduced pressure. The residue was dissolved in toluene (~20 mL) then loaded on to a Biotage automated chromatography system (2 stacked 220 g and one 330 g silica gel cartridges), eluting with a gradient of 0-25% toluene in hexanes. The recovered product (2.2 g, 73% yield) was filtered through basic alumina (450 g), eluting with 50% dichloromethane in hexanes. The recovered solid (2.1 g) was dissolved in dichloromethane (40 mL) then precipitated with methanol (260 mL) to give bis[1-(2,6-bis(propan-2-yl-d₇ )phenyl)-2-(4-(methyl-d₃ )phenyl-2'-yl)-1H-benzo[d]imid-azol-3-yl]-[(2-(dibenzo[b,d]furan-4-yl)-3'-yl)-4-(4-(2,2-dimethylpropyl-1,1-d₂)-phenyl)pyridin-1-yl)iridium(III) (1.98 g, 99.6% UPLC purity) as a red-orange solid.

Synthesis Example 10

[Ir(4,5-bis(methyl-d ₃)-2-(4-(methyl-d ₃)phenyl)pyridine(-1H))₂(MeOH)₂] tri-fluoromethanesulfonate

To a solution of di-µ-chloro-tetrakis [κ2(C2,N)-4,5-bis(metyl-d ₃)-2-(4-(methyl-d ₃)-phenyl)pyridine]diiridium(III) (106 g 122 mmol, 1.0 equiv) in dichloromethane (2.0 L), in a flask wrapped with foil to exclude light, was added a solution of silver trifluoromethanesulfonate (69.3 g, 270 mmol, 2.2 equiv) in methanol (500 mL). The reaction mixture was stirred overnight at RT under nitrogen. The reaction mixture was filtered through a pad of silica gel pad (300 g) topped with Celite^® (20 g), rinsing with dichloromethane (1.0 L). The filtrate was concentrated under reduced pressure and the residue dried in a vacuum oven to give [Ir(4,5-bis(methyl-d ₃)-2-(4-(methyl-d ₃)phenyl)pyndine(-1H))₂(MeOH)₂] trifluoromethanesulfonate (~162.5 g, 81% yield) as a yellow solid.

Mer-Bis[2-(4-(methyl-d₃ )phenyl-2'-yl)-4,5-bis(methyl-d₃ )pyridin-1-yl][2-((di-benzo[b,d]furan-4-yl)-3'-yl)-4-(4-(2,2-dimethylpropyl-1,1-d₂ )phenyl)-pyridin-1-yl]iridium(III)

A nitrogen flushed 500 mL 4-neck flask was charged with [Ir(4,5-bis(methyl-d₃ )-2-(4-(methyl-d₃ )phenyl)-pyridine(-H))₂(MeOH)₂](trifluoromethanesulfonate) (6.5 g, 7.97 mmol, 1.0 equiv) and 2-(dibenzo[b,d]furan-4-yl)-4-(4-(2,2-dimethylpropyl-1,1-d₂ )phenyl)-pyridine (3.5 g, 8.85 mmol, 1.1 equiv) and acetone (160 mL). The mixture was sparged with nitrogen for 15 minutes and the flask wrapped in foil to exclude light. Triethylamine (3.33 mL, 23.9 mmol, 3.0 equiv) was added then the reaction mixture was heated at 50 °C overnight. After 18 hours, the reaction mixture was cooled to RT, filtered through a pad of Celite^® (20 g) and the filtrate was concentrated under reduced pressure. The residue was triturated with 10% dichloromethane in methanol (60 mL). The solid was filtered and washed with methanol (50 mL) to give mer-complex (7.2 g, 88% HPLC purity, 87% Q NMR purity) as an orange solid.

Bis[2-(4-(methyl-d₃ )phenyl-2'-yl)-4,5-bis(methyl-d₃ )pyridin-1-yl][2-((dibenzo[b,d]furan-4-yl)-3'-yl)-4-(4-(2,2-dimethylpropyl-1,1-d₂ )phenyl)pyridin-1-yl]iridium(III)

The meridonal isomer was converted to the facial isomer via photoisomerization.

Purification

Crude product after photo reaction (~8 g) was filtered through a 2 inch pad of silica gel (~50 g) topped with a 6 inch pad of basic alumina (~200 g), eluting with 50% dichloromethane in hexanes (1 L). Product fractions were concentrated under reduced pressure. The residue was dissolved in dichloromethane, adsorbed onto Celite^® (14.7 g) and purified on a Biotage Isolera automated chromatography system (3 stacked 100 g Biotage HC silica gel cartridges), eluting with 0-17% tetrahydrofuran in hexanes. Pure product fractions were concentrated under reduced pressure. The residue was dissolved dichloromethane (20 mL) and precipitated with methanol (50 mL). The solid was filtered and washed with methanol (30 mL) to give bis[2-(4-(methyl-d₃ )phenyl-2'-yl)-4,5-bis(methyl-d₃ )-pyridin-1-yl][2-((dibenzo[b,d]furan-4-yl)-3'-yl)-4-(4-(2,2-di-methylpropyl-1,1-d₂ )-phenyl)pyridin-1-yl]iridium(III) (2.9 g, 36% yield, 99.8% UPLC purity) as a bright yellow solid.

Synthesis Example 11

Di-µ-chloro-tetrakis[k2(C2,N)-1-(2,6-bis(propan-2-yl-d₇ )phenyl)-2-(4-(methyl-d₃ )phenyl-2'-yl)-1H-benzo[d]imidazol-3-yl]diiridium(III)

A mixture of 1-(2,6-bis(propan-2-yl-d₇ )phenyl)-2-(4-(methyl-d₃ )phenyl)-1H-benzo-[d]imidazole (7 g, 18.21 mmol, 2.2 equiv) and iridium(III) chloride hydrate (2.62 g, 8.28 mmol, 1.0 equiv) in 2-ethoxyethanol (90 mL) and water (30 mL) was heated at 102 °C for 70 hours. The cooled reaction mixture was filtered, the solid washed with methanol (3 × 50 mL) then dried in a vacuum oven for a few hours at ~50 °C to give di-µ-chlorotetrakis[k2(C2,N)-1-(2,6-bis-(propan-2-yl-d₇ )phenyl)-2-( 4-(methyl-d₃ )phenyl-2'-yl)-1H-benzo[d]imid-azol-3-yl]-diiridium (III) (7.08 g, 86% yield) as a yellow solid.

[Ir(1-(2,6-bis(propan-2-yl-d₇ )phenyl)-2-(4-(methyl-d₃ )phenyl-2'-yl)-1H-benzo-[d]imidazol-3-yl)(1H)₂(MeOH)₂] trifluoromethanesulfonate

A solution of silver trifluoromethanesulfonate (1.85 g, 7.21 mmol, 2.2 equiv) in methanol (18 mL) was added in one portion to a solution of di-µ-chloro-tetrakis-[k2(C2,N)-1-(2,6-bis(propan-2-yl-d₇ )phenyl)-2-(4-(methyl-d₃ )phenyl-2'-yl)-1H-benzo[d]imidazol-3-yl]diiridium (III) (7 g, 3.26 mmol, 1.0 equiv) in dichloromethane (90 mL) and the flask wrapped with foil to exclude light. The reaction mixture was stirred at RT overnight under nitrogen. The reaction mixture was filtered through a short (~1 inch) pad of silica gel, rinsing with dichloromethane (2 × 100 mL) then a 5:1 mixture of dichloromethane and methanol (2 × 100 mL). The filtrate was concentrated under reduced pressure and the residue dried in a vacuum oven at 50 °C overnight to give [Ir(1-(2,6-bis-(propan-2-yl-d₇ )phenyl)-2-(4-(methyl-d₃ )phenyl-2'-yl)-1H-benzo[d]imidazol-3-yl)-(1H)₂(MeOH)₂] trifluoromethanesulfonate (7.9 g, 103% yield) as a yellow-green solid.

Bis[1-(2,6-bis(propan-2-yl-d₇ )phenyl)-2-(4-(methyl-d₃ )phenyl-2'-yl)-1H-benzo-[d]imidazol-3-yl][4-(4-(2,2-dimethylpropyl-1,1-d₂ )phenyl)-2-(phenyl-2'-yl)pyri-din-1-yl]iridium(III)

A mixture of [Ir(1-(2,6-bis-(propan-2-yl-d₇ )phenyl)-2-(4-(methyl-d₃ )phenyl-2'-yl)-1H-benzo[d]imidazol-3-yl)-(1H)₂-[MeOH)₂] trifluoromethanesulfonate (2.63 g, 2.24 mmol, 1.0 equiv), 4-(4-(2,2-dimethylpropyl-1,1-d₂ )phenyl)-2-phenylpyridine (0.68 g, 2.24 mmol, 1.0 equiv) and 2,6-lutidine (0.24 g, 2.24 mmol, 1.0 equiv) in ethanol (40 mL) was heated at 78 °C for 40 hours. The cooled reaction mixture was concentrated under reduced pressure. The residue was purified on a Buchi automated chromatography system (220 g and 330 g stacked silica gel cartridges), eluting with a gradient of 0-20-25% dichloromethane in hexanes. The recovered product (1.7 g, 98% UPLC purity) was re-purified on a Buchi automated chromatography system (6 stacked 120 g silica gel cartridges), eluting with a gradient of 0-20-25% dichloromethane in hexanes. The recovered product (1.4 g) was filtered through basic alumina (450 g), eluting with 50% dichloromethane in hexanes. The recovered solid (1.3 g) was dissolved in dichloromethane (2 mL) and precipitated with methanol (250 mL). The solid was filtered and dried in a vacuum oven at ~50 °C overnight to give bis[1-(2,6-bis(pro-pan-2-yl-d₇ )phenyl)-2-(4-(methyl-d₃ )phenyl-2'-yl)-1H-benzo[d]imidazol-3-yl] [4-(4-(2,2-dimethylpropyl-1, 1-d₂ )phenyl)-2-(phenyl-2'-yl)pyridin-1-yl]iridium(III) (1.25 g, 44% yield, 99.9% UPLC purity) as a red-orange solid.

Device Fabrications

All device examples were fabricated by high vacuum (<10^-7 Torr) thermal evaporation (VTE). The anode electrode was 800 Å of indium tin oxide (ITO). The cathode consisted of 10 Å of LiQ (8-quinolinolato lithium) followed by 1000 Å of Al. All devices were encapsulated with a glass lid sealed with an epoxy resin in a nitrogen glove box (< 1 ppm of H₂O and O₂) immediately after fabrication, and a moisture getter was incorporated inside the package.
The organic stack of the device examples consisted of sequentially, from the ITO surface, 100 Å of HATCN as the hole injection layer (HIL), 450 Å of hole transport material HTM as the hole transport layer (HTL), 50 Å of EBL as an electron blocking layer (EBL), 400 Å of 10 wt% emitter doped in a host as the emissive layer (EML) wherein the host comprised a 60/40 wt% mixture of H1/H2, and 350 Å of 35% ETM in LiQ as the electron transport layer (ETL). As used herein, HATCN, HTM, EBL, H1, H2, and ETM have the following structures.

Device structure is shown in the Table 1 and the chemical structures of the device materials are shown below.

Table 1. Device example layer structure

Layer	Material	Thickness [Å]
Anode	ITO	1,150
HIL	HAT-CN	100
HTL	HTM	450
EBL	EBL	50
EML	H1/H2 (6:4): Emitter (wt% as noted in Table 2)	400
ETL	Liq:ETM 35%	350
EIL	Liq	10
Cathode	A1	1,000

Example	Emitter	wt %	Maximum emission wavelengh [nm]	At 1,000 nits
Example	Emitter	wt %	Maximum emission wavelengh [nm]	EQE (%)	LE [cd/A]
Example 1	YD1	10	559	29.0	96.2
Example 2	CE1	10	558	27.6	91.7
Example 3	YD2	10	561	29.8	97.9
Example 4	CE2	10	561	27.7	90.5
Example 5	YD3	10	561	30.6	101.6
Example 6	CE3	10	562	28.5	92.3
Example 7	YD4	10	558	26.7	91.3
Example 8	CE4	10	561	26.6	89.0

It can be seen from the device data in Table 2 that the inventive emitter compounds (YD1 to YD4) all have better EQE and higher luminance efficacy (LE) than their counterpart comparative compounds (CE1 to CE4) under same device testing conditions. The inventive emitter compounds were unexpectedly more efficient than their comparative compounds, and these increases were beyond any value that could be attributed to experimental error and the observed improvements were significant.

The present invention is further defined by the following numbered aspects:
1. A heteroleptic compound having a Formula Ir(L_A)_m(L_B)_3-m, having a structure of

wherein:
m is 1 or 2; moieties A, C, and D are each independently a monocyclic ring or a polycyclic fused ring structure, both comprising 5-membered and/or 6-membered aromatic rings; each of R^A, R^B, R^C, R^D, and R^E independently represents mono to the maximum allowable substitution, or no substitution; each R¹, R², R^A, R^B, R^C, R^D, and R^E is independently hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, boryl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; wherein if moiety A is a monocyclic 6-membered ring, then the R^A para to N of ring A is not an aryl group; wherein L_A and L_B are different; and at least one of R¹ and R² is selected from the group consisting of aryl, heteroaryl, cycloalkyl, heterocycloalkyl, and combinations thereof; and two adjacent R^B, one R^A and one R^B, one R^E and one R^D, or two adjacent R¹, R² and R^E can be joined to form a ring.
2. The compound of aspect 1, wherein each R¹, R², R^A, R^B, R^C, R^D, and R^E is independently hydrogen or a substituent selected from the group consisting of deuterium, fluorine, alkyl, cycloalkyl, heteroalkyl, alkoxy, aryloxy, amino, silyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, aryl, heteroaryl, nitrile, isonitrile, sulfanyl, and combinations thereof.
3. The compound of aspect 1, wherein R¹ is selected from the group consisting of aryl, heteroaryl, cycloalkyl, heterocycloalkyl, and combinations thereof.
4. The compound of aspect 1, wherein R² is selected from the group consisting of aryl, heteroaryl, cycloalkyl, heterocycloalkyl, and combinations thereof.
5. The compound of aspect 1, wherein at least one of R¹ and R² is a substituted or unsubstituted group selected from the group consisting of phenyl, pyridine, pyrimidine, pyridazine, pyrazine, and triazine.
6. The compound of aspect 1, wherein at least one of R¹ and R² is a para-substituted 6-membered ring.
7. The compound of aspect 1, wherein each of R¹ and R² can be further independently substituted by a moiety selected from the group consisting of LIST 1 as defined herein before.
8. The compound of aspect 1, wherein at least one R^A, one R^B, one R^C, one R^D, or one R^E is deuterium, alkyl, or a combination of both.
9. The compound of aspect 1, wherein moiety D is a monocyclic aromatic ring, or a polycyclic fused aromatic ring structure.
10. The compound of aspect 1, wherein moiety A is pyridine, imidazole or benzimidazole.
11. The compound of aspect 1, wherein moiety C comprises a 5-membered ring.
12. The compound of aspect 1, wherein the ligand L_A is selected from the group consisting of:

wherein Xa is selected from the group consisting of O, S, NR, CR'R", and SiR'R"; wherein Xb is selected from the group consisting of O, S, and NR; and wherein each of R, R', and R" is independently hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, boryl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof.
13. The compound of aspect 1, wherein the ligand L_A is selected from L_Ai, wherein i is an integer from 1 to 79, and L_A1 to L_A79 have the structures as defined in LIST 2 herein before.
14. The compound of aspect 13, ligand L_B is selected from the group consisting of L_B1-1 to L_B399-39 defined by naming convention L_Bk-h, wherein k is an integer from 1 to 399, and h is an integer from 1 to 39;
wherein each of L_Bk-1 to L_Bk-39 is defined as follows:

L_Bk-1 has the following structure	L_Bk-2 has the following structure	L_Bk-3 has the following structure

L_Bk-4 has the following structure	L_Bk-5 has the following structure	L_Bk-6 has the following structure

L_Bk-7 has the following structure	L_Bk-8 has the following structure	L_Bk-9 has the following structure

L_Bk-10 has the following structure	L_Bk-11 has the following structure	L_Bk-12 has the following structure

L_Bk-13 has the following structure	L_Bk-14 has the following structure	L_Bk-15 has the following structure

L_Bk-16 has the following structure	L_Bk-17 has the following structure	L_Bk-18 has the following structure

L_Bk-19 has the following structure	L_Bk-20 has the following structure	L_Bk-21 has the following structure

L_Bk-22 has the following structure	L_Bk-23 has the following structure	L_Bk-24 has the following structure

L_Bk-25 has the following structure	L_Bk-26 has the following structure	L_Bk-27 has the following structure
	and
L_Bk-28 has the following structure	L_Bk-29 has the following structure	L_Bk-30 has the following structure

L_Bk-31 has the following structure	, L_Bk-32 has the following structure	L_Bk-33 has the following structure

L_Bk-34 has the following structure	, L_Bk-35 has the following structure	L_Bk-36 has the following structure

L_Bk-37 has the following structure	, L_Bk-38 has the following structure	L_Bk-39 has the following structure

wherein, for each k from 1 to 399, R^F and R^G are defined as follows:

; wherein R¹ to R⁶⁷ have the structures as defined in LIST 5 herein before.
15. The compound of aspect 14, wherein the compound has a Formula Ir(L_Ai)(L_Bk-h)₂, or a Formula Ir(L_Ai)₂(L_Bk-h).
16. The compound of aspect 1, wherein the compound is selected from the group consisting of the compounds of LIST 6 as defined herein before.
17. An organic light emitting device (OLED) comprising:

an anode;
a cathode; and
an organic layer disposed between the anode and the cathode, wherein the organic layer comprises a heteroleptic compound as defined in any one of the previous aspects, having a Formula Ir(L_A)_m(L_B)_3-m, having a structure of
wherein:
m is 1 or 2; moieties A, C, and D are each independently a monocyclic ring or a polycyclic fused ring structure, both comprising 5-membered and/or 6-membered aromatic rings; each of R^A, R^B, R^C, R^D, and R^E independently represents mono to the maximum allowable substitution, or no substitution; each R¹, R², R^A, R^B, R^C, R^D, and R^E is independently hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, boryl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; wherein if moiety A is a monocyclic 6-membered ring, then the R^A para to N of ring A is not an aryl group; wherein L_A and L_B are different; and at least one of R¹ and R² is selected from the group consisting of aryl, heteroaryl, cycloalkyl, heterocycloalkyl, and combinations thereof; and two adjacent R^B, one R^A and one R^B, one R^E and one R^D, or two adjacent R¹, R² and R^E can be joined to form a ring.

an anode;
a cathode; and
an organic layer disposed between the anode and the cathode, wherein the organic layer comprises a heteroleptic compound as defined in any one of aspects 1 to 16, having a Formula Ir(L_A)_m(L_B)_3-m, having a structure of
wherein:
m is 1 or 2; moieties A, C, and D are each independently a monocyclic ring or a polycyclic fused ring structure, both comprising 5-membered and/or 6-membered aromatic rings; each of R^A, R^B, R^C, R^D, and R^E independently represents mono to the maximum allowable substitution, or no substitution; each R¹, R², R^A, R^B, R^C, R^D, and R^E is independently hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, boryl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; wherein if moiety A is a monocyclic 6-membered ring, then the R^A para to N of ring A is not an aryl group; wherein L_A and L_B are different; and at least one of R¹ and R² is selected from the group consisting of aryl, heteroaryl, cycloalkyl, heterocycloalkyl, and combinations thereof; and two adjacent R^B, one R^A and one R^B, one R^E and one R^D, or two adjacent R¹, R² and R^E can be joined to form a ring.

Claims

A heteroleptic compound having a Formula Ir(L_A)_m(L_B)_3-m, having a structure of
wherein:
m is 1 or 2;

moieties A, C, and D are each independently a monocyclic ring or a polycyclic fused ring structure, both comprising 5-membered and/or 6-membered aromatic rings;

each of R^A, R^B, R^C, R^D, and R^E independently represents mono to the maximum allowable substitution, or no substitution;

each R¹, R², R^A, R^B, R^C, R^D, and R^E is independently hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, boryl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof;

wherein if moiety A is a monocyclic 6-membered ring, then the R^A para to N of ring A is not an aryl group;

wherein L_A and L_B are different; and

at least one of R¹ and R² is selected from the group consisting of aryl, heteroaryl, cycloalkyl, heterocycloalkyl, and combinations thereof; and

two adjacent R^B, one R^A and one R^B, one R^E and one R^D, or two adjacent R¹, R² and R^E can be joined to form a ring.
The compound of claim 1, wherein R¹ is selected from the group consisting of aryl, heteroaryl, cycloalkyl, heterocycloalkyl, and combinations thereof, and/or wherein R² is selected from the group consisting of aryl, heteroaryl, cycloalkyl, heterocycloalkyl, and combinations thereof.
The compound of claim 1 or 2, wherein at least one of R¹ and R² is a substituted or unsubstituted group selected from the group consisting of phenyl, pyridine, pyrimidine, pyridazine, pyrazine, and triazine.
The compound of any one of claims 1 to 3, wherein at least one of R¹ and R² is a para-substituted 6-membered ring.
The compound of any one of claims 1 to 4, wherein at least one R^A, one R^B, one R^C, one R^D, or one R^E is deuterium, alkyl, or a combination of both.
The compound of any one of claims 1 to 5, wherein moiety D is a monocyclic aromatic ring, or a polycyclic fused aromatic ring structure.
The compound of any one of claims 1 to 6, wherein moiety A is pyridine, imidazole or benzimidazole.
The compound of any one of claims 1 to 7, wherein moiety C comprises a 5-membered ring.
The compound of claim 1, wherein the ligand L_A is selected from the group consisting of:

wherein Xa is selected from the group consisting of O, S, NR, CR'R", and SiR'R";

wherein Xb is selected from the group consisting of O, S, and NR; and

wherein each of R, R, and R" is independently hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, boryl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof.
The compound of claim 1, wherein the ligand L_A is selected from L_Ai, wherein i is an integer from 1 to 79, and L_A1 to L_A79 have the following structures:

and
The compound of claim 10, ligand L_B is selected from the group consisting of L_B1-1 to L_B399-39 defined by naming convention L_Bk-h, wherein k is an integer from 1 to 399, and h is an integer from 1 to 39;
wherein each of L_Bk-1 to L_Bk-39 is defined as follows: L_Bk-1 has the following structure L_Bk-2 has the following structure L_Bk-3 has the following structure

L_Bk-4 has the following structure L_Bk-5 has the following structure L_Bk-6 has the following structure

L_Bk-7 has the following structure L_Bk-8 has the following structure L_Bk-9 has the following structure

L_Bk-10 has the following structure L_Bk-11 has the following structure L_Bk-12 has the following structure

L_Bk-13 has the following structure L_Bk-14 has the following structure L_Bk-15 has the following structure

L_Bk-16 has the following structure L_Bk-17 has the following structure L_Bk-18 has the following structure

L_Bk-19 has the following structure L_Bk-20 has the following structure L_Bk-21 has the following structure

L_Bk-22 has the following structure L_Bk-23 has the following structure L_Bk-24 has the following structure

L_Bk-25 has the following structure L_Bk-26 has the following structure L_Bk-27 has the following structure

L_Bk-28 has the following structure L_Bk-29 has the following structure L_Bk-30 has the following structure

L_Bk-31 has the following structure , L_Bk-32 has the following structure L_Bk-33 has the following structure

L_Bk-34 has the following structure , L_Bk-35 has the following structure L_Bk-36 has the following structure

L_Bk-37 has the following structure , L_Bk-38 has the following structure L_Bk-39 has the following structure

wherein, for each k from 1 to 399, R^F and R^G are defined as follows: k R^F R^G k R^F R^G k R^F R^G 1 R¹ R¹ 134 R²⁶ R¹ 267 R³⁰ R¹ 2 R¹ R² 135 R²⁶ R² 268 R³⁰ R² 3 R¹ R³ 136 R²⁶ R³ 269 R³⁰ R³ 4 R¹ R⁴ 137 R²⁶ R⁴ 270 R³⁰ R⁴ 5 R¹ R⁵ 138 R²⁶ R⁵ 271 R³⁰ R⁵ 6 R¹ R⁶ 139 R²⁶ R⁶ 272 R³⁰ R⁶ 7 R¹ R⁷ 140 R²⁶ R⁷ 273 R³⁰ R⁷ 8 R¹ R⁸ 141 R²⁶ R⁸ 274 R³⁰ R⁸ 9 R¹ R⁹ 142 R²⁶ R⁹ 275 R³⁰ R⁹ 10 R¹ R¹⁰ 143 R²⁶ R¹⁰ 276 R³⁰ R¹⁰ 11 R¹ R¹¹ 144 R²⁶ R¹¹ 277 R³⁰ R¹¹ 12 R¹ R¹² 145 R²⁶ R¹² 278 R³⁰ R¹² 13 R¹ R¹³ 146 R²⁶ R¹³ 279 R³⁰ R¹³ 14 R¹ R¹⁴ 147 R²⁶ R¹⁴ 280 R³⁰ R¹⁴ 15 R¹ R¹⁵ 148 R²⁶ R¹⁵ 281 R³⁰ R¹⁵ 16 R¹ R¹⁶ 149 R²⁶ R¹⁶ 282 R³⁰ R¹⁶ 17 R¹ R¹⁷ 150 R²⁶ R¹⁷ 283 R³⁰ R¹⁷ 18 R¹ R¹⁸ 151 R²⁶ R¹⁸ 284 R³⁰ R¹⁸ 19 R¹ R¹⁹ 152 R²⁶ R¹⁹ 285 R³⁰ R¹⁹ 20 R¹ R²⁰ 153 R²⁶ R²⁰ 286 R³⁰ R²⁰ 21 R¹ R²¹ 154 R²⁶ R²¹ 287 R³⁰ R²¹ 22 R¹ R²² 155 R²⁶ R²² 288 R³⁰ R²² 23 R¹ R²³ 156 R²⁶ R²³ 289 R³⁰ R²³ 24 R¹ R²⁴ 157 R²⁶ R²⁴ 290 R³⁰ R²⁴ 25 R¹ R²⁵ 158 R²⁶ R²⁵ 291 R³⁰ R²⁵ 26 R¹ R²⁶ 159 R²⁶ R²⁶ 292 R³⁰ R²⁶ 27 R¹ R²⁷ 160 R²⁶ R²⁷ 293 R³⁰ R²⁷ 28 R¹ R²⁸ 161 R²⁶ R²⁸ 294 R³⁰ R²⁸ 29 R¹ R²⁹ 162 R²⁶ R²⁹ 295 R³⁰ R²⁹ 30 R¹ R³⁰ 163 R²⁶ R³⁰ 296 R³⁰ R³⁰ 31 R¹ R³¹ 164 R²⁶ R³¹ 297 R³⁰ R³¹ 32 R¹ R³² 165 R²⁶ R³² 298 R³⁰ R³² 33 R¹ R³³ 166 R²⁶ R³³ 299 R³⁰ R³³ 34 R¹ R³⁴ 167 R²⁶ R³⁴ 300 R³⁰ R³⁴ 35 R¹ R³⁵ 168 R²⁶ R³⁵ 301 R³⁰ R³⁵ 36 R¹ R³⁶ 169 R²⁶ R³⁶ 302 R³⁰ R³⁶ 37 R¹ R³⁷ 170 R²⁶ R³⁷ 303 R³⁰ R³⁷ 38 R¹ R³⁸ 171 R²⁶ R³⁸ 304 R³⁰ R³⁸ 39 R¹ R³⁹ 172 R²⁶ R³⁹ 305 R³⁰ R³⁹ 40 R¹ R⁴⁰ 173 R²⁶ R⁴⁰ 306 R³⁰ R⁴⁰ 41 R¹ R⁴¹ 174 R²⁶ R⁴¹ 307 R³⁰ R⁴¹ 42 R¹ R⁴² 175 R²⁶ R⁴² 308 R³⁰ R⁴² 43 R¹ R⁴³ 176 R²⁶ R⁴³ 309 R³⁰ R⁴³ 44 R¹ R⁴⁴ 177 R²⁶ R⁴⁴ 310 R³⁰ R⁴⁴ 45 R¹ R⁴⁵ 178 R²⁶ R⁴⁵ 311 R³⁰ R⁴⁵ 46 R¹ R⁴⁶ 179 R²⁶ R⁴⁶ 312 R³⁰ R⁴⁶ 47 R¹ R⁴⁷ 180 R²⁶ R⁴⁷ 313 R³⁰ R⁴⁷ 48 R¹ R⁴⁸ 181 R²⁶ R⁴⁸ 314 R³⁰ R⁴⁸ 49 R¹ R⁴⁹ 182 R²⁶ R⁴⁹ 315 R³⁰ R⁴⁹ 50 R¹ R⁵⁰ 183 R²⁶ R⁵⁰ 316 R³⁰ R⁵⁰ 51 R¹ R⁵¹ 184 R²⁶ R⁵¹ 317 R³⁰ R⁵¹ 52 R¹ R⁵² 185 R²⁶ R⁵² 318 R³⁰ R⁵² 53 R¹ R⁵³ 186 R²⁶ R⁵³ 319 R³⁰ R⁵³ 54 R¹ R⁵⁴ 187 R²⁶ R⁵⁴ 320 R³⁰ R⁵⁴ 55 R¹ R⁵⁵ 188 R²⁶ R⁵⁵ 321 R³⁰ R⁵⁵ 56 R¹ R⁵⁶ 189 R²⁶ R⁵⁶ 322 R³⁰ R⁵⁶ 57 R¹ R⁵⁷ 190 R²⁶ R⁵⁷ 323 R³⁰ R⁵⁷ 58 R¹ R⁵⁸ 191 R²⁶ R⁵⁸ 324 R³⁰ R⁵⁸ 59 R¹ R⁵⁹ 192 R²⁶ R⁵⁹ 325 R³⁰ R⁵⁹ 60 R¹ R⁶⁰ 193 R²⁶ R⁶⁰ 326 R³⁰ R⁶⁰ 61 R¹ R⁶¹ 194 R²⁶ R⁶¹ 327 R³⁰ R⁶¹ 62 R¹ R⁶² 195 R²⁶ R⁶² 328 R³⁰ R⁶² 63 R¹ R⁶³ 196 R²⁶ R⁶³ 329 R³⁰ R⁶³ 64 R¹ R⁶⁴ 197 R²⁶ R⁶⁴ 330 R³⁰ R⁶⁴ 65 R¹ R⁶⁵ 198 R²⁶ R⁶⁵ 331 R³⁰ R⁶⁵ 66 R¹ R⁶⁶ 199 R²⁶ R⁶⁶ 332 R³⁰ R⁶⁶ 67 R¹ R⁶⁷ 200 R²⁶ R⁶⁷ 333 R³⁰ R⁶⁷ 68 R² R¹ 201 R¹ R²⁶ 334 R¹ R³⁰ 69 R³ R¹ 202 R² R²⁶ 335 R² R³⁰ 70 R⁴ R¹ 203 R³ R²⁶ 336 R³ R³⁰ 71 R⁵ R¹ 204 R⁴ R²⁶ 337 R⁴ R³⁰ 72 R⁶ R¹ 205 R⁵ R²⁶ 338 R⁵ R³⁰ 73 R⁷ R¹ 206 R⁶ R²⁶ 339 R⁶ R³⁰ 74 R⁸ R¹ 207 R⁷ R²⁶ 340 R⁷ R³⁰ 75 R⁹ R¹ 208 R⁸ R²⁶ 341 R⁸ R³⁰ 76 R¹⁰ R¹ 209 R⁹ R²⁶ 342 R⁹ R³⁰ 77 R¹¹ R¹ 210 R¹⁰ R²⁶ 343 R¹⁰ R³⁰ 78 R¹² R¹ 211 R¹¹ R²⁶ 344 R¹¹ R³⁰ 79 R¹³ R¹ 212 R¹² R²⁶ 345 R¹² R³⁰ 80 R¹⁴ R¹ 213 R¹³ R²⁶ 346 R¹³ R³⁰ 81 R¹⁵ R¹ 214 R¹⁴ R²⁶ 347 R¹⁴ R³⁰ 82 R¹⁶ R¹ 215 R¹⁵ R²⁶ 348 R¹⁵ R³⁰ 83 R¹⁷ R¹ 216 R¹⁶ R²⁶ 349 R¹⁶ R³⁰ 84 R¹⁸ R¹ 217 R¹⁷ R²⁶ 350 R¹⁷ R³⁰ 85 R¹⁹ R¹ 218 R¹⁸ R²⁶ 351 R¹⁸ R³⁰ 86 R²⁰ R¹ 219 R¹⁹ R²⁶ 352 R¹⁹ R³⁰ 87 R²¹ R¹ 220 R²⁰ R²⁶ 353 R²⁰ R³⁰ 88 R²² R¹ 221 R²¹ R²⁶ 354 R²¹ R³⁰ 89 R²³ R¹ 222 R²² R²⁶ 355 R²² R³⁰ 90 R²⁴ R¹ 223 R²³ R²⁶ 356 R²³ R³⁰ 91 R²⁵ R¹ 224 R²⁴ R²⁶ 357 R²⁴ R³⁰ 92 R²⁶ R¹ 225 R²⁵ R²⁶ 358 R²⁵ R³⁰ 93 R²⁷ R¹ 226 R²⁷ R²⁶ 359 R²⁶ R³⁰ 94 R²⁸ R¹ 227 R²⁸ R²⁶ 360 R²⁷ R³⁰ 95 R²⁹ R¹ 228 R²⁹ R²⁶ 361 R²⁸ R³⁰ 96 R³⁰ R¹ 229 R³⁰ R²⁶ 362 R²⁹ R³⁰ 97 R³¹ R¹ 230 R³¹ R²⁶ 363 R³¹ R³⁰ 98 R³² R¹ 231 R³² R²⁶ 364 R³² R³⁰ 99 R³³ R¹ 232 R³³ R²⁶ 365 R³³ R³⁰ 100 R³⁴ R¹ 233 R³⁴ R²⁶ 366 R³⁴ R³⁰ 101 R³⁵ R¹ 234 R³⁵ R²⁶ 367 R³⁵ R³⁰ 102 R³⁶ R¹ 235 R³⁶ R²⁶ 368 R³⁶ R³⁰ 103 R³⁷ R¹ 236 R³⁷ R²⁶ 369 R³⁷ R³⁰ 104 R³⁸ R¹ 237 R³⁸ R²⁶ 370 R³⁸ R³⁰ 105 R³⁹ R¹ 238 R³⁹ R²⁶ 371 R³⁹ R³⁰ 106 R⁴⁰ R¹ 239 R⁴⁰ R²⁶ 372 R⁴⁰ R³⁰ 107 R⁴¹ R¹ 240 R⁴¹ R²⁶ 373 R⁴¹ R³⁰ 108 R⁴² R¹ 241 R⁴² R²⁶ 374 R⁴² R³⁰ 109 R⁴³ R¹ 242 R⁴³ R²⁶ 375 R⁴³ R³⁰ 110 R⁴⁴ R¹ 243 R⁴⁴ R²⁶ 376 R⁴⁴ R³⁰ 111 R⁴⁵ R¹ 244 R⁴⁵ R²⁶ 377 R⁴⁵ R³⁰ 112 R⁴⁶ R¹ 245 R⁴⁶ R²⁶ 378 R⁴⁶ R³⁰ 113 R⁴⁷ R¹ 246 R⁴⁷ R²⁶ 379 R⁴⁷ R³⁰ 114 R⁴⁸ R¹ 247 R⁴⁸ R²⁶ 380 R⁴⁸ R³⁰ 115 R⁴⁹ R¹ 248 R⁴⁹ R²⁶ 381 R⁴⁹ R³⁰ 116 R⁵⁰ R¹ 249 R⁵⁰ R²⁶ 382 R⁵⁰ R³⁰ 117 R⁵¹ R¹ 250 R⁵¹ R²⁶ 383 R⁵¹ R³⁰ 118 R⁵² R¹ 251 R⁵² R²⁶ 384 R⁵² R³⁰ 119 R⁵³ R¹ 252 R⁵³ R²⁶ 385 R⁵³ R³⁰ 120 R⁵⁴ R¹ 253 R⁵⁴ R²⁶ 386 R⁵⁴ R³⁰ 121 R⁵⁵ R¹ 254 R⁵⁵ R²⁶ 387 R⁵⁵ R³⁰ 122 R⁵⁶ R¹ 255 R⁵⁶ R²⁶ 388 R⁵⁶ R³⁰ 123 R⁵⁷ R¹ 256 R⁵⁷ R²⁶ 389 R⁵⁷ R³⁰ 124 R⁵⁸ R¹ 257 R⁵⁸ R²⁶ 390 R⁵⁸ R³⁰ 125 R⁵⁹ R¹ 258 R⁵⁹ R²⁶ 391 R⁵⁹ R³⁰ 126 R⁶⁰ R¹ 259 R⁶⁰ R²⁶ 392 R⁶⁰ R³⁰ 127 R⁶¹ R¹ 260 R⁶¹ R²⁶ 393 R⁶¹ R³⁰ 128 R⁶² R¹ 261 R⁶² R²⁶ 394 R⁶² R³⁰ 129 R⁶³ R¹ 262 R⁶³ R²⁶ 395 R⁶³ R³⁰ 130 R⁶⁴ R¹ 263 R⁶⁴ R²⁶ 396 R⁶⁴ R³⁰ 131 R⁶⁵ R¹ 264 R⁶⁵ R²⁶ 397 R⁶⁵ R³⁰ 132 R⁶⁶ R¹ 265 R⁶⁶ R²⁶ 398 R⁶⁶ R³⁰ 133 R⁶⁷ R¹ 266 R⁶⁷ R²⁶ 399 R⁶⁷ R³⁰

;wherein R¹ to R⁶⁷ have the following structures:
The compound of claim 11, wherein the compound has a Formula Ir(L_Ai)(L_Bk-h)₂, or a Formula Ir(L_Ai)₂(L_Bk-h).
The compound of claim 1, wherein the compound is selected from the group consisting of:

and
An organic light emitting device comprising:
an anode;

a cathode; and

an organic layer disposed between the anode and the cathode, wherein the organic layer comprises a heteroleptic compound as defined in any one of claims 1 to 13.
A consumer product comprising an organic light-emitting device as defined in claim 14.